Document NEz6oe1vKeXOzJr3yvnGraZM8

Science /11AAAS Supplementary Materials for Low-temperature mineralization of perfluorocarboxylic acids Brittany Trang et al. Corresponding authors: K. N. Houk, M@chem.ucla.edu; William R. Dichtel, Science 377, 839 (2022) DOI: 10.1126/science.abm8868 The PDF file includes: @northwestern.edu Materials and Methods Supplementary Text Figs. Si to S66 Tables Si to S4 Data Si References Materials and Methods Materials Reagents were purchased in reagent grade from commercial suppliers and used without further purification, unless otherwise described. Anhydrous DMSO was obtained by drying with activated 4 molecular sieves. Reagents were purchased from Fisher or Sigma unless specified. 4,4-difluorobenzophenone NMR standard (Merck) was prepared by diluting to 0.095 M in DMSO-d6 and adding 60-80 L of solution to a coaxial NMR tube insert (Wilmad-Lab Glass, WGS-5BL). Each 19F NMR sample was referenced to 4,4-difluorobenzophenone (-106.5 ppm) by inserting the coaxial tubes containing the external NMR standard into the NMR sample tube before NMR analysis. 13C NMR samples were quantified using a sodium acetate standard in D2O (50 L, 5.33 M). 1H NMR samples were quantified using 4,4-dihydroxybiphenyl dissolved in DMSO-d6 (0.68 M). Quantification of samples was conducted by integrating each NMR peak and normalizing with the external standard peak integration, then converting to molar concentration using the known molar amount of the external standard. 25 mL PTFE round bottom flasks were purchased from Ace Glass (United States, 13438-16). PFCA degradation reactions were conducted on 0.5 mmol or 1 mmol scales. Instruments Proton nuclear magnetic resonance (1H NMR) spectra and fluorine nuclear magnetic resonance (19F NMR) spectra were recorded at 25 C on a 400 MHz Bruker Avance III HD Nanobay equipped with a BBFO Smart probe w/ Z-Gradient (unless stated otherwise). Fluorinedecoupled carbon nuclear magnetic resonance (13C NMR) spectra and two-dimensional C-F spectra were recorded on a Bruker Neo 600 MHz system with a QCI-F cryoprobe w/ Z-Gradient. Quantitative 13C NMR spectra were recorded on a Bruker Avance III 500 MHz system equipped with a 5mm DCH CryoProbe w/Z-Gradient using a 40 second D1 delay. Other spectra were recorded on a Bruker Avance III 600 MHz with a BBFO Smart Probe w/ Z-Gradient. Experiments used pulse programs adapted from standard Bruker pulses library. Ion chromatography was performed using a Thermo Scientific Dionex ICS-5000+ equipped with a Dionex AS-DV autosampler and using a Dionex IonPac AS22 column (Product No. 064141, Thermo Scientific, California, USA). The analysis was run using an eluent of 4.5 mM sodium carbonate and 1.4 mM sodium bicarbonate (Product No. 063965 from Thermo Scientific, California, USA) and a Dionex AERS 500 Carbonate 4 mm Electrolytically Regenerated Suppressor (Product No 085029 from Thermo Scientific, California, USA). A flow rate of 1.2 mL/min was used, giving the following retention times: fluoride = 3.3 min; formate = 3.8 min. Elemental standards containing 1000 g/mL F-, and 1000 ug/mL HCOO- (ICF1, ICHCO1, respectively, from Inorganic Ventures, Christiansburg, VA, USA) were mixed to make quantitative standards consisting of 50, 25, 12.5, 6.25, 3.125, 1.56, 0.78 ug/mL of each anion in ultra-pure H2O (18.2 Mcm). Ultra pure H2O was used as the calibration blank. Validation experiments indicated an error of approximately 10% for ion chromatography results. APCI-MS was collected on an Agilent 6545 QTOF Mass Spectrometer equipped with Atmospheric Pressure Chemical Ionization (APCI) source coupled with Agilent 1200 series LC running in direct injection mode. Data acquisition and analysis were done on Agilent Mass Hunter software. GC/MS analysis was performed in the Reactor Engineering and Catalyst Testing (REACT) core facility at Northwestern University using an Agilent 6850 GC system coupled to an Agilent 5975C MS system. Helium (Airgas, 99.999%) was purified using an Agilent "Big Universal Trap" 2 (Model RMSH-2) and used as a carrier gas. Gas separation was performed using a HP-Plot Q column (19091P-Q04E, 30m x 0.320 mm x 20 um) starting at 50 C for 4 minutes. The temperature was then ramped to 220 C at 30 C/min and held for 3 minutes. The flow rate of He was maintained at 1.2 mL/min (inlet split ratio of 10:1). The MS was operated in scan mode (Gain factor = 1, EM voltage = 2518, MS Source = 250 C, MS Quad = 150 C) from m/z = 5 to m/z = 300. A solvent delay was not used. Kinetic traces for PFOA degradation at different temperatures were fitted to the equation y = ae-x/b + c in MATLAB using the Curve Fitting application. Geometry optimizations, frequency analyses, and single-point energies were calculated at the theoretical M06-2X/6-311+G(2d,p)-SMD-(DMSO) level (36, 37) using the Gaussian 16 package (38) with default convergence criteria. M06-2X functional gives refined energies for organic systems (39). Frequency outcomes were examined to confirm stationary points as minima (no imaginary frequencies) or transition states (only one imaginary frequency). Paton's GoodVibes (40) was used to correct entropy and enthalpy by Grimme's quasi-harmonic approximation (41) and Head-Gordon's method (42). 3D structures of molecules were generated by CYL view (43). All energies are in kcal/mol if not labeled otherwise. All bond lengths are in Angstroms (). 3 Synthetic Procedures and NMR Characterization of Synthesized Compounds General PFCA Destruction Procedure: Perfluorooctanoic acid (207 mg, 0.500 mmol) and sodium hydroxide (0.600 g, 15.0 mmol) were added to a 25 mL PTFE round bottom flask along with a PTFE-coated magnetic stirbar. 5 mL DMSO was added to the reaction vessel, followed by 0.625 mL distilled or de-ionized water. The vessel was sonicated for approximately 15 seconds, then the t = 0 aliquot was taken by diluting a 50 L aliquot into 500 L of deuterated solvent. The vessels were sealed with a rubber septum and pierced with a needle that was left in the septum to prevent overpressure. The vented vessels were then added to an oil bath preheated to 120 C and stirred at 500 RPM for the specified time, usually 24 hours. Liquid aliquots for reactions monitored over time were taken using a syringe inserted through the rubber septum and diluted as above with solids removed by centrifugation if necessary. The reactions were removed from the heat and cooled for at least 40 minutes before workup. The entire contents of the reaction were diluted with distilled or deionized water until the solids at the bottom were completely dissolved (typically 20- 40 mL water added) and were transferred to a polypropylene centrifuge tube. The resulting fluoride- and formate- containing solution was further diluted in water 100x-500x for ion chromatography analysis. For carbonaceous products quantification, the contents of the reaction were added to a 15 mL polypropylene centrifuge tube, centrifuged, and the DMSO solvent was decanted. The remaining solids were rinsed and centrifuged 2x with dichloromethane, then dried overnight at 120 C on high vac. A portion of the solids (~30 mg) was dissolved (750 L D2O + 50 L NaOAc standard in D2O) for quantitative 13C NMR analysis. Scheme S1 General procedure to decarboxylate perfluorocarboxylic acids and synthesis of perfluoro-1Hheptane (2). PFOA (1.035 g, 2.500 mmol) was added to a glass pressure vessel with PTFE screwtop and PTFE-coated magnetic stirbar and dissolved in a mixture of DMSO (5.00 mL) and deionized H2O (0.625 mL). The solution was heated to 120 C for 41 h, then was removed from heat and allowed to cool to room temperature for 2 h. The product phase-separated as a clear liquid on the bottom of the vessel and was decanted via micropipette to provide 2 as a colorless oil (0.703 g, 76% yield). 19F NMR (564 MHz, DMSO) -83.614, -123.990, -124.648, -125.218, -128.289, 131.643, -140.332. 13C NMR (151 MHz, DMSO) 116.223, 109.800, 109.315, 109.196, 109.152 (d, J2CH = 7.5 Hz), 107.548, 107.498, 106.194 (d, J1CH = 197.7 Hz). 1H NMR (400 MHz, DMSO) 5.94 (tt, J = 51.4, 5.1 Hz, 1H). 4 Scheme S2 Perfluoro-1H-hexane (S1). S1 was obtained using the above procedure as a colorless oil (0.654 g, 84% yield). 19F NMR (564 MHz, DMSO) -83.73 (tt, J = 10.4, 2.4 Hz), -124.955, -125.559, 128.487, -131.875, -140.31 (d, J = 51.7 Hz). 13C NMR (151 MHz, DMSO) 116.282, 109.757, 109.340, 109.13 (d, J = 6.6 Hz), 107.560, 106.81 (d, J = 195.8 Hz). 1H NMR (600 MHz, DMSO) 5.85 (tt, J = 51.7, 5.1 Hz, 1H). 5 Supplementary Text Experimental Determination of G Using the Eyring equation: = - where is the transmission coefficient, assumed to be 1 in this case kB is the Boltzmann constant (1.38 x 10-23 J/K) T is the temperature in Kelvin h is Planck's constant (6.626 x 10-34 Js) G is the Gibbs energy of activation R is the gas constant (8.3145 J/molK, or 1.987 cal/molK) G393 = 30.0 kcal/mol 6 Quantification of Carbon-Containing Byproducts Quantitative 13C NMR spectroscopy of the precipitate accounted for almost all of the carbon-containing species generated by the PFOA degradation reaction, none of which contain C- F bonds besides trifluoroacetate ions (Table S4). The byproducts were identified as a distribution of one-carbon (carbonate, formate), two-carbon (oxalate, glycolate, trifluoroacetate), and threecarbon products (tartronate). Quantification by 13C NMR spectroscopy of the precipitate and 1H NMR spectroscopy of the reaction solution indicated 2.5 0.3 equivalents of formate per mol of PFOA starting material (Table S4). The formate ions were independently quantified by ion chromatography and corresponded to 2.1 0.2 equivalents of formate per mol of PFOA starting material (Figure 2D). There are several potential pathways for the generation of some of these carbon-containing products that are not further explored in this work. However, the formation of non-fluorinated, relatively oxidized 1-3 carbon products is generally consistent with the proposed mechanism, while accounting for all of the carbon balance of the PFOA degradation reaction. One Carbon Products: Under the basic reaction conditions, the carbon dioxide reacts with excess hydroxide ions to provide sodium carbonate within the precipitate. 2.1 0.3 equivalents of carbonate ions per mol of PFOA were detected by quantitative 13C NMR spectroscopy. 2.5 0.3 equivalents of formate per mol PFOA were detected, as measured by 1H NMR spectroscopy of the liquid reaction mixture and 13C NMR spectroscopy of the precipitate. It should be noted that the carbonate ion concentration could not be independently measured by ion chromatography because available IC capabilities were run in carbonate-based buffers, precluding the detection of this ion. Two Carbon Products: 0.32 0.04 mols of trifluoroacetate per mol of PFOA were detected by 19F NMR spectroscopy of the reaction solution at 24 h reaction time; only trace CF3CO2- was found in the precipitate by 19F NMR spectroscopy. 0.6 0.1 mols of glycolate ions per mol of PFOA were detected, some of which might be formed from the degradation of fluoroacetic acid, which was observed in low-temperature experiments (see main text). Oxalate ions were detected at concentrations corresponding to 0.7 0.1 mols per mol of PFOA. Three Carbon Products: We assign another carbon-containing product as sodium tartronate (0.2 0.1 equiv per mol PFOA) based on its 13C NMR resonance at 177 ppm, which correlates with a 1H NMR resonance at 4.2 ppm (Fig. S32). These chemical shifts match literature reports (29, 44), and the correlation is consistent with an intermediate we propose in the mechanism (Figure 3). We propose that tartronate is formed in pathway D because it was observed in greater amounts in the degradation of PFBA (C = 4), likely from hydrolysis of INT8 (Figure 3). Unidentified Product: An unidentified product (4.9 2.4 mol% C) is likely derived from the reaction of glycolic acid with another intermediate in the pathway, as it was formed in higher concentration when glycolic acid and PFOA were subjected to the degradation conditions together. However, the unknown product did not form when glycolic acid was subjected to the degradation conditions in the absence of PFOA. The unidentified compound has two 13C NMR resonances, one at 177.9 ppm and one at 69.4 ppm (Fig. S30). The two resonances integrate 1:1 with each other, making it likely that it contains either two or four carbons. Further analysis of the reaction precipitates from degrading the C = 2, 4, 5, and 6 acids (Fig. S30) showed that the presence of oxalate was correlated with the presence of TFA, but it is not a direct degradation product of TFA, whose only carbon-containing degradation products were carbonate ions. The amount of oxalate appeared to increase slightly for PFCA with longer perfluoroalkyl chains, such that we speculate that it is formed, at least in part, within the B/C pathways, as are formate ions. Once the fluorocarbon intermediate is protonated, though, as in 7 INT31 (Figure 3), it is difficult to get the correct oxidation state for oxalate except through Cannizzaro reactivity or disproportionation, which could be possible under the extremely basic reaction conditions. We think it is likely that the oxalate either originates from a process in the B pathway preceding INT31 or from further degradation of carbonaceous byproducts. 8 Computational Mechanistic Investigations of PFCA Degradation As shown in Fig. S44, decarboxylation is the rate-determining step of thermolysis with an energy barrier of 27.7 kcal/mol. This is also consistent with the experimental conditions that decarboxylation requires 120C to initiate. Relaxed-scan comparisons of the decarboxylation energy profiles in both gas and liquid phase show that the solvent effect plays a significant role (Fig. S45). The energy profile in the liquid phase has a maximum value, while the energy profile in the gas phase keeps rising, indicating that in the gas phase, the products formed by decarboxylation will return to the reactant with a very low energy barrier. Hydroxide in the solvent may play a significant role in promoting decarboxylation. Perfluoroanion INT1 can eliminate a fluoride to become a perfluoroalkene INT2 or be protonated by water to become a polyfluoroalkane. Since SN2 reactions on saturated fluoroalkane carbons require a high energy barrier (Fig. S46), INT1 is more likely to generate perfluoroalkene INT2. The resulting alkene INT2 is easily hydroxylated; our calculations also suggest that the hydroxylation is specifically favored at the terminal position, As shown in Fig. S47, the relaxedscan addition energy profiles on the internal side and the terminal side show that the addition on the internal side of the alkene has a barrier of 8.9 kcal/mol, whereas addition on the terminal side does not have an enthalpic barrier. After the formation of hydroxylated perfluoroanion INT3, two consecutive fluoride ion eliminations produce ,-unsaturated acyl fluoride INT6. The carbon-oxygen bond length scanning coordinates of INT7 and INT13 do not have inflection points but continuously rise, showing that neither 1,2-addition nor 1,4-addition have enthalpic barriers (Fig. S48). 1,4-addition produces 1,3-diketone compound INT8. Fig. S49 shows that subsequent hydroxide addition is favored to occur on the ketone carboxyl side of INT8 rather than the acyl fluoride side. While 1,4-addition leads to the formation of shorter PFCAs such as CF3CO2- (Fig. S44), 1,2-addition can lead to the eventual formation of byproduct HCOOH. The 1,2-hydroxylation produces , unsaturated perfluorocarboxylic acid INT14 (Fig. S51), then generates an alkene anion INT30. Several pathways for generating INT30 from INT14 exist (Fig. S50). We propose two possible pathways for the transformation of INT14 to INT30 (Fig. S50). In Pathway B (Fig. S54), hydroxide addition to the alpha carbon allows an acid fluoride equivalent of oxalate to be generated, eliminating a fluoroalkene anion five carbons in length (for PFOA; generalized to other PFCAs, the alkene is three carbons shorter than the original PFCA length) with a barrier of 24.8 kcal/mol. In Pathway B (Fig. S51, Fig. S52), 1,4 addition of the hydroxide to INT14 leads to a Darzens-type decarboxylation through an epoxide intermediate INT19 via TS11 with a barrier of 19.4 kcal/mol. Interestingly, though carbonate INT18 has a similar structure to acid fluoride INT9, they have different reactivity (Fig. S53). INT9 tends to fragment, while INT18 tends to form the epoxide because it cannot form a dianion through fragmentation. For longer PFCAs (original PFCA C > 6), the unsaturated aldehyde intermediate can eliminate a fluoride and pass through a Pathway C-like process (Pathway C; Fig. S52) where hydroxide adds to the carbonyl and eliminates off an alkene four carbons shorter than the original PFCA (for PFOA, four carbons in length) and an equivalent of glyoxylate, which can disproportionate into an equivalent of oxalate and an equivalent of glycolate (45). The mechanisms explicitly proposed in Fig. S50 and its supporting figures show many classes of reactivity at the possible bifurcation points. For example, the C and C reactivity modes are the same, even though the resulting byproducts are different; similarly, pathway D-type retro- 9 aldol reactions could occur at other 1,3-dicarbonyl intermediates to create a PFCA + carboxylic acid byproduct equivalent. We expect that the reactivity motifs we have explored through computation may be active at intermediates in the mechanism other than what we have explicitly shown. Calculation results show that protonating the alkene anion INT30 is more favorable than eliminating a fluoride to generate the alkyne, the hydroxide addition is more likely to happen on the terminal side of INT31 (Fig. S56) as it was for the fully fluorinated INT2, and solvent effects can reduce the energy barrier for protonation (Fig. S58). Likewise, two consecutive eliminations of fluoride ions generates ,-unsaturated aldehyde INT35, an analogue to the ,-unsaturated acid fluoride INT6. The scanning coordinates of carbon-oxygen bonds length of INT36 and INT37 show that neither 1,2-addition or 1,4-addition to INT35 have enthalpic barriers (Fig. S57). The 1,2-addition leads to the production of formate through elimination (Fig. S55), while the 1,4-addition can exit the cycle and generate shorter PFCAs through pathway D (Figure 3, S59). As with analogue INT8, hydroxide addition is more favorable on the ketone carboxyl side of 1,3-diketone compound INT38 (Fig. S60). 10 Computational Investigations Into Alternate Mechanisms Finally, to show that the mechanism we proposed is the most reasonable at present, we calculated the -lactone mechanism proposed by Pellerite (33) and a difluorocarbene mechanism we proposed. Selecting some intermediates to calculate the energy, we found that neither of these hypothetical mechanisms are feasible for our system (Fig. S61 and Fig. S62). 11 Computational Mechanistic Investigations of PFECA Degradation We also used computational tools to investigate the GenX degradation pathway. GenX goes through a mechanism much like Pathway A for PFCAs before forming INT45 (Fig. S63). However, INT45 cannot eliminate a fluoride like PFCAs. Instead, sequential hydrolysis reactions generate 5, which was experimentally observed. 5 does not easily decarboxylate (Fig. S65). Instead, it is attacked by hydroxide and eliminates a perfluoroether tail, which can be transformed into a corresponding PFCA through hydrolysis in pathway F (Fig. S64). Fig. S66 shows which side of 5 hydroxide more easily attacks. 12 Fig. S1. 19F NMR spectra of PFOA (top, DMSO-d6, 400 MHz) and 2 (bottom, DMSO-d6, 600 MHz). 2 is insoluble in DMSO, so it was analyzed as a neat oil in an inner coaxial insert tube with a solution of a 4,4-difluorobenzophenone standard (-106.5 ppm) dissolved in DMSO-d6 in an outer tube. 13 Fig. S2. Fluorine-decoupled 13C NMR spectrum of perfluoro-1H-heptane, calibrated to DMSOd6 (39.52 ppm). 2 is insoluble in DMSO, and so it was analyzed as a neat oil in an inner coaxial insert tube with a solution of a 4,4-difluorobenzophenone standard (-106.5 ppm) dissolved in DMSO-d6 in an outer tube. 14 Fig. S3. 1H NMR spectrum of perfluoro-1H-heptane (DMSO-d6, 600 MHz). 2 is insoluble in DMSO, so it was analyzed as a neat oil in an inner coaxial insert tube with a solution of a 4,4difluorobenzophenone standard (7.3-7.8 ppm, marked with X) dissolved in DMSO-d6 in an outer tube. 15 Fig. S4. 19F-13C HSQC spectrum of perfluoro-1H-heptane used to assign the 13C resonances. The 19F resonances were assigned by comparison to PFOA. 16 Fig. S5. 19F NMR spectra of perfluoro-1H-hexane (DMSO-d6, 600 MHz). S1 is insoluble in DMSO, and so it was analyzed as a neat oil in an inner coaxial insert tube with a solution of a 4,4-difluorobenzophenone standard (-106.5 ppm) dissolved in DMSO-d6 in an outer tube. 17 Fig. S6. Fluorine-decoupled 13C NMR spectrum of perfluoro-1H-hexane, calibrated to DMSO-d6 (39.52 ppm). S1 neat in coaxial insert tube with 4,4-difluorobenzophenone standard dissolved in DMSO-d6 in outer tube. 18 Fig. S7. 1H NMR spectrum of perfluoro-1H-hexane (DMSO-d6, 600 MHz). S1 is insoluble in DMSO, so it was analyzed as a neat oil in an inner coaxial insert tube with a solution of a 4,4difluorobenzophenone standard (7.3-7.8 ppm, marked with X) dissolved in DMSO-d6 in an outer tube. 19 Fig. S8. 19F-13C HSQC of perfluoro-1H-hexane used to assign carbon peaks. Fluorine peaks assigned based on PFOA and literature. 20 Fig. S9. 1H NMR spectra to monitor formate ion formation at 120C as a function of reaction time. Peaks highlighted in gray correspond to the 4,4-difluorobenzophenone external standard, and peaks highlighted red correspond to formate ions. A) PFOA degradation reaction: the formate ion concentration increases steadily over the course of the reaction, even after all PFOA has been degraded (24 h) and only TFA remains. B) Control reaction of water, DMSO, and NaOH in the absence of PFOA demonstrates a slower background reaction that also produces a small amount of formate, presumably from the degradation of the DMSO solvent. In both cases, formate production was confirmed by ion chromatography. However, 1H NMR spectroscopy is not sufficient for formate quantification, as much of the formate precipitates out of the reaction and cannot be detected in solution. 21 Fig. S10. Appearance and disappearance of perfluoropropionic acid (PFPrA) during the degradation of PFOA at 120C as a function of reaction time. Bottom spectrum: authentic sample of PFPrA and NaOH heated to 120C for 1 h. Blue highlighted peaks correspond to trifluoroacetate (TFA), green highlighted peaks correspond to PFOA, and yellow highlighted peaks correspond to PFPrA. PFPrA is observed as a trace byproduct (in the 10 h spectrum, its concentration is approximately 1-2% of the initial PFOA concentration) that subsequently degrades between reaction times of 24-57 h. 22 Fig. S11. 19F NMR (565 MHz, DMSO) spectrum of concentrated aliquot of PFPrA degradation reaction (30 equiv NaOH in 8:1 DMSO:H2O). The degradation of PFPrA provides evidence for the formation of a volatile protodecarboxylated fluorocarbon CF3CF2H, along with difluoroacetate ions. CF2HCOO- Actual: -121.66 (d, J = 53.5 Hz) Literature (46): (solvent not specified): -123.63 d, J = 56.5 Hz. CF3CF2H Actual: -85.00 (s, 3F), -139.44 (d, J = 51.4 Hz, 2F). Literature (47): (CD3)2SO: -139.5 (2F, dq, 2JHF = 51.1, 3JFF = 3.0 Hz, HCF2), -85.1 (3F, dt, 3JHF = 3JFF = 3.0 Hz, CF3). Unidentified peaks at -85.04 (s), -140.07 (s) 23 Fig. S12. 1H NMR (600 MHz, DMSO) spectrum of concentrated aliquot of PFPrA degradation reaction (30 eq. NaOH in 8:1 DMSO:H2O). The degradation of PFPrA provides evidence for the formation of a volatile protodecarboxylated fluorocarbon CF3CF2H, along with difluoroacetate ions. CF2HCOO- Actual: 6.92 (t, J = 50.8 Hz) Literature (48): (CF2HCOOH, 299.949 MHz, solvent not specified): 1H spectrum: 6.13 ppm, 2JH,F = 53.10 Hz. CF3CF2H Actual: 5.56 (t, J = 55.8 Hz) Literature (49): (neat, referenced to DMSO in D2O) 5.80(1H,tq,J=52.31,2.55Hz) 24 Fig. S13. 19F NMR spectra (600 MHz) of aliquots from the 40C degradation of PFHp-1H. When the degradation is run at this lower temperature, various fluorinated intermediates (fluoroacetic acid, INT8/9, perfluoropentanoic acid) are observed that are not seen in the spectra of degradation reactions run at higher temperatures. These intermediates are shown in greater detail below. TFA = trifluoroacetate, ES = external standard (4,4-difluorobenzophenone), FAA = fluoroacetic acid. 25 Fig. S14. Partial 19F NMR spectra (600 MHz) of the 40C degradation of 2. In the first few hours of reaction, an intermediate with 3 CF2 groups is observed (purple). We hypothesize that this intermediate is INT8 or 9; see Fig. S15 for further assignment of these peaks. In spectra obtained at 24 h, 77 h, and 142 h, resonances corresponding to five-carbon PFPeA are observed (orange), in accordance with the three-carbon shortening process proposed in Figure 3 Pathways A + D. 26 Fig. S15. Proposed assignment of 19F NMR peaks corresponding to proposed intermediates INT8 or 9 from the 19F NMR spectrum of 1 h aliquot of 40C degradation of 2. TFA = trifluoroacetate, x = 4,4-difluorobenzophenone standard. Peak assignments marked with colored dots based on the spectrum of PFPeA and the assignment of enol fluorine (50). While the relative peak positions are relatively consistent with the proposed structures, the peak integrations and couplings are potentially inconsistent with these structures. 27 Fig. S16. 19F NMR spectra (600 MHz) of aliquots from the 40 C degradation of S1. When the degradation is run at this lower temperature, various fluorinated intermediates (fluoroacetic acid, INT8/9, perfluorobutanoic acid) are observed that are not seen in the spectra of degradation reactions run at higher temperatures. These intermediates are shown in greater detail below. TFA = trifluoroacetate, ES = external standard (4,4-difluorobenzophenone), FAA = fluoroacetic acid. 28 Fig. S17. Partial 19F NMR spectra (600 MHz) degradation of S1 performed at 40C. In the first few hours of reaction, an intermediate with 3 CF2 groups is observed (purple). We hypothesize that this intermediate is INT8 or 9; see Fig. S18 for further assignment of these peaks. In spectra obtained at 24 h, 77 h, and 142 h, resonances corresponding to four-carbon PFBA are observed (blue), in accordance with the three-carbon shortening process proposed in Figure 3 Pathways A + D. A peak corresponding to perfluoropropionic acid (PFPrA) is highlighted in yellow. 29 Fig. S18. Proposed assignment of 19F NMR peaks corresponding to proposed intermediates INT8 or 9 from the 19F NMR spectrum of 1 h aliquot of 40C degradation of S1. TFA = trifluoroacetate, x = 4,4-difluorobenzophenone standard. Peak assignments marked with colored dots based on the spectrum of PFBA and the assignment of enol fluorine (50). While the relative peak positions are relatively consistent with the proposed structures, the peak integrations and couplings are potentially inconsistent with these structures. 30 Fig. S19. 19F NMR spectra of aliquots of perfluorooctanesulfonic acid potassium salt (PFOSK, 0.089 M) in DMSO:H2O (8:1) in the presence of NaOH (30 equiv) and heated to 120C. 4,4difluorobenzophenone was used as an external standard (X). No degradation of PFOSK is observed, implicating decarboxylation as the first step of PFCA degradation under these conditions. 31 Fig. S20. 19F NMR spectra of 0.089 M perfluorooctanoic acid (PFOA) in water with 30 equiv NaOH heated to 120C. No change in the spectra over time shows that this decarboxylation needs polar aprotic solvent to occur. 4,4'-difluorobenzophenone standard is crossed out. 32 Fig. S21. Disappearance of PFOA over time at three different reaction temperatures as measured by 19F NMR. [PFOA] = 0 mmol at < 24 h at 120C (average of triplicates), 100 h at 100C (average of triplicates), and >290 h for 80C, showing the high temperature-dependence of the rate-limiting step. 33 Fig. S22. Rates of PFCA degradation, as measured by 19F NMR integration of the respective alpha-carbon fluorine resonances of each PFCA. 34 Fig. S23. Kinetic trace of mols of trifluoroacetate per mol of reactant PFCA, as measured by 19F NMR spectroscopy. For TFA itself, the plot indicates its degradation rate. For PFPrA and PFBA, little or no TFA is formed. For PFCAs with five or more carbons, approximately 0.3 mol TFA/mol PFCA are formed in the early stages of the degradation reaction. 35 Fig. S24. Kinetic trace of the degradation of CF3CO2Na over time as calculated by NMR concentration. CF3CO2Na (0.089 M in DMSO) was degraded at 120C with 30 equiv NaOH in 8:1 DMSO:H2O. 36 Fig. S25. Fitted curve for degradation of PFOA at 120C as calculated from the integral of F2 in the 19F NMR over time. Data is average of triplicate runs (see Fig. S21). 37 Fig. S26. Fitted curve for degradation of PFOA at 100C as calculated from the integral of F2 in the 19F NMR over time. Data is average of triplicate runs (see Fig. S21). 38 Fig. S27. Fitted curve for degradation of PFOA at 90C as calculated from the integral of F2 in the 19F NMR over time. Data is average of duplicate runs. 39 Fig. S28. Fitted curve for degradation of PFOA at 80C as calculated from the integral of F2 in the 19F NMR over time. Data from single trial. 40 Fig. S29. Fluorine balance of PFOA degradation performed at 120C at different reaction times. Organofluorine content (black dashed line) was measured by integrating all 19F NMR peaks; the fluoride ion (black solid line) were measured by ion chromatography of entire reaction solution. The total fluorine (gray line) is calculated by adding the organofluorine and fluoride ion amounts and remains close to unity throughout the PFOA degradation reaction, indicating little to no loss of volatile organofluorine products. 41 Fig. S30. Quantitative 13C NMR of isolated reaction precipitate dissolved in D2O [sodium acetate was used as an internal standard, (50 L of a 0.68 M solution in D2O). The PFOA sample was recorded with 900 scans at 40 s delay. Samples other than PFOA were recorded with 300 scans at 40 s delay and have imperfect proton decoupling from the extreme pH sample conditions. Sodium trifluoroacetate (TFA) shows only carbonate (168 ppm) as reaction byproduct. PFBA shows carbonate, trace oxalate ion formation, and enhanced tartronate ion formation compared to other samples. PFPeA shows glycolate (180 ppm, 61 ppm), tartronate, oxalate, and carbonate ion formation. PFHxA shows glycolate, oxalate, formate (present in proton NMR, ion chromatography, hard to see here due to proton coupling), and carbonate. PFOA shows glycolate, tartronate, oxalate, formate, carbonate, and two trace unknown peaks at 178 and 69 ppm. *Tartronate assigned based on literature references (29, 44). 42 Fig. S31. HSQC of isolated PFOA reaction precipitate dissolved in D2O with 30 L DMSO standard allows for identification of some carbonaceous byproducts 43 Fig. S32. HMBC of isolated PFOA reaction precipitate dissolved in D2O with 30 L DMSO standard allows for identification of some carbonaceous byproducts. 44 Fig. S33. 19F NMR spectra of GenX degradation reaction at 120C. The starting material (added as GenX ammonium salt) quickly decarboxylates and proto-de-trifluoromethylates to intermediate 5, which was also detected by ESI-MS (Fig. S42). Over the course of several hours, 5 degrades to PFPrA, which subsequently degrades further, mainly to CF3CF2H, as described for the degradation of PFPrA (Figure 2, Fig. S37). 45 Fig. S34. 19F NMR spectra of 4 degradation reaction at 120C. The starting material (added as 4 ammonium salt) quickly decarboxylates and proto-de-trifluoromethylates to intermediate S2, which was also detected by APCI-MS (Fig. S43). Over the course of several hours, S2 degrades to PFPeA, which subsequently degrades further, mainly to fluoride and CF3CO2-, as described for the degradation of PFPeA (Figure 2). 46 Fig. S35. 19F NMR spectra of degradation of GenX over time at increasing temperature stages. Starting material for GenX (top, shaded dots) disappear as GenX is converted to compound 5 and falls out of solution, presumably because of an insoluble intermediate that is converted to intermediate 5 over time, causing 5 to slowly increase in concentration (brightly colored dots, until 120 h). When the temperature is increased to 80C (121 h), peaks corresponding to PFPrA (brown dots) appear from 5 degradation as predicted, then disappear more quickly after the temperature is increased to 120C (289 h). 47 Fig. S36. 19F NMR spectra of degradation of 4 over time at increasing temperature stages. Starting material for 4 (top, shaded dots) disappear as 4 is converted to intermediate S2 and falls out of solution, presumably because of an insoluble intermediate that is converted to intermediate S2 over time, causing S2 to slowly increase in concentration (brightly colored dots, until 120 h). When the temperature is increased to 80C (121 h), peaks corresponding to PFPeA (brown dots) and trifluoroacetate appear from S2 degradation as predicted, then disappear more quickly after the temperature is increased to 120 C (289 h). 48 Fig. S37. 19F NMR spectra of the degradation of perfluoropropionic acid (top) after 22 hours and GenX (bottom) after 24 hours at 120C. Peaks corresponding to the same compounds appear in the degradation of each, indicating that GenX degrades to PFPrA and then follows the PFPrA degradation pathway, including producing CF3CF2H, which volatilizes and does not defluorinate, resulting in a lower fluoride recovery than for longer-chain analogues. Identity of CF3CF2D hypothesized. 49 Fig. S38. APCI-MS spectrum of an aliquot of PFOA degradation reaction diluted in acetonitrile after 4 hours of heating at 120C. 50 Fig. S39. APCI-MS spectrum of an aliquot of PFPrA degradation reaction diluted in acetonitrile after 4 hours of heating at 120C. The prominent 118.9930 m/z peak identified in this reaction mixture is consistent with the proposed reaction mechanism as it corresponds to CF3CF2-, which either comes from the decarboxylation of CF3CF2CO2- or the deprotonation of CF3CF2H. 51 Fig. S40. GCMS-headspace total ion chromatograms after 4 hours of reaction for GenX (top), perfluoropropionic acid (second from top), 4 (second from bottom), perfluoropentanoic acid (bottom). Both PFPrA and GenX show evidence of CF3CF2+ gas fragments, presumably derived from CF3CF2H, whereas PFPeA and 4 show only CF3+ fragments, presumably from an equilibrium between CF3COOH and CF3H. 52 Fig. S41. APCI-MS spectrum of an aliquot of GenX degradation reaction diluted in acetonitrile after 7 hours of heating at 120C. Molecular species identified from this reaction mixture are consistent with the proposed reaction mechanism, especially the prominent 118.9930 m/z peak corresponding to CF3CF2-, which either comes from the decarboxylation of CF3CF2CO2- or the deprotonation of CF3CF2H. 53 Fig. S42. ESI-MS of spectrum of an aliquot of GenX degradation reaction diluted in acetonitrile after 2 hours of heating at 120C. Molecular species identified from this reaction mixture are consistent with the proposed reaction mechanism, especially the 5 and 5 dimer at 260.71 m/z and 522.91 m/z. 54 Fig. S43. APCI-MS spectrum of an aliquot of 4 degradation reaction diluted in acetonitrile after 4 hours of heating at 120C. Molecular species identified from this reaction mixture are consistent with the proposed reaction mechanism, especially the S2 and S2 dimer peaks at 360.9746 m/z and 722.9564 m/z. 55 Fig. S44. Gibbs free energy profile for pathways A and D, X = F. 56 Fig. S45. A) The scanning coordinates of C-C bond length to show solvent effect in decarboxylation. The bond is colored pink. B) 3D structure of TS1. 57 Fig. S46. A) Comparison of -elimination and protonation of INT1. An SN2 reaction on a saturated fluoroalkane carbon requires a high energy barrier (29.7 kcal/mol). B) 3D structures of TS7 and TS2. 58 Fig. S47. A) Comparison of hydroxide addition on the internal side and the external side of the alkene. While hydroxide addition on the terminal side has a inflection point, addition on the internal side has no enthalpic barrier. B) 3D structure of TS8. 59 Fig. S48. The scanning coordinates of the carbon-oxygen bonds of INT7 and INT13. When gradually increasing the carbon-oxygen bond length, the energy does not have an inflection point but continuously rises, indicating that 1,2-addition and 1,4-addition both do not have enthalpic barriers. 60 Fig. S49. A) Comparison of hydroxide addition on the acyl fluoride side and the ketone carbonyl side of INT8. B) 3D structures of TS9 and TS5. 61 Fig. S50. Proposed pathways for converting INT14 to INT30 and forming carbon byproducts. 62 Fig. S51. Gibbs free energy profile for pathway B (), ending with decarboxylation. 63 Fig. S52. Gibbs free energy profile for pathways B () + pathway C. 64 Fig. S53. A) Comparison of epoxide formation and the fragmentation of INT9 (acid fluoride). B) Comparison of epoxide formation and the fragmentation of INT18 (carboxylate). C) 3D structures of TS6, TS17, TS11, TS18. 65 Fig. S54. Gibbs free energy profile for pathway B. 66 Fig. S55. Gibbs free energy profile for pathway C. 67 Fig. S56. A) Comparison of -elimination and protonation of INT30. B) Comparison of hydroxide addition on the internal side and the terminal side. C) 3D structures of TS26, TS27 and TS22. 68 Fig. S57. The scanning coordinates of carbon-oxygen bond of INT36 and INT37, also indicating that 1,2-addition and 1,4-addition both have no enthalpic barrier. 69 Fig. S58. Comparison of protonation in solvent and in gas phase (energy in the blue parentheses). 70 Fig. S59. Gibbs free energy profile for pathway D, X=H. 71 Fig. S60. A) Comparison of hydroxide addition on the aldehyde side and the ketone carbonyl side of INT38. B) 3D structures of TS30 and TS28. 72 Fig. S61. A) -lactone mechanism proposed by Pellerite (33) and calculated by Ge et al. (34). B) The Gibbs free energy change for selected intermediate indicates that this mechanism is not feasible. 73 Fig. S62. A) Mechanism proposed previously assuming that difluorocarbene is the key intermediate. B) The Gibbs free energy change for selected intermediate indicates that this mechanism is not feasible. 74 Fig. S63. Gibbs free energy profile for pathways A and E for GenX. 75 Fig. S64. Gibbs free energy profile for pathway F for GenX. 76 Fig. S65. Comparison of hydroxide attack vs. decarboxylation of 5. The transition state for the transformation of 5 to INT51 will be higher than the energy of INT51, which is already 33.8 higher than 5, disfavoring the reaction compared to TS37 (21.9 kcal/mol relative to 5) and INT48 (-61.8 kcal/mol relative to 5). 77 Fig. S66. Comparison of hydroxide attack on different sides of compound 5. 78 Table S1. Emerging PFAS Destruction Methods. Ref. Matrix/ Time, Technique Reagents Substrates (Temp, Conc No. Press.) (9) Sonication 5 ppm MQ PPFFOOAS, 120m-in180 PFpOpSm, 5 PFOA Result > 90% F- Specific Drawbacks Proposed Mechanism Desulfonylation > alkene > - difluoroCcaFr3breandei,caClF, > CO, CO2, F- Evidence for Mechanism GC-MS headspace See puRbeliclaatteiodns Overall Drawbacks "Designing an effective ultrasound reactor has proven to be one of the most challenging aspects for the application of Figure 3 (10) scohnaollelynsgisesininwtahteerotpretiamtmizaetniot nduoef otoperating conditions and parameters such as frequency and power"; matrix components may also reduce efficiency (20) NaCl, PFOA, 5 mg/L F- per 8.3 mg/L PFAS adsorbed to the reactor (11) Plasma aqueous PFOS 120 min 8.3 ppm orig PFOA (60%); 4.4 (~20-40%), many short-chain mg/L F- for PFOS (53%) PFAS byproducts formed DHEH None Figure 7 - - Electrochemical, 100 mg.L (12) Ti/RuO2 NaCl, 1500 mg/L Na SO 24 PFOA, PFOS Quantifying the removal of PFOA due to electrochemical 6 h 5 ppm 98% FF-- ffoorr PPFFOOSA, 58% dtirffeicautmlt etontdveetersrmusinseo;rPptFioOnA sorption in zero-current control = 67% None N/A Se3c.t3ion - (21) ETlei/cStrnoOch2-eSmbi-cBail, 1.4 g/L NaClO4 PFOA 63.8% F-, observation High energy consumption; DHEH, O2 generation from Mostly proposed, water as O source 3 h 50 ppm of distribution of smaller oxidation of other matrix two perfluoroalcohol [C4F9(18O)]- supported by 18O tests, - PFCAs components radicals one MS peak. 2.9 ppm (13) ElectroBcDhDemical, DMI wNaate2Sr,O04.1 PFBS, PFHxS, PFOS PFBS, 45% PFBS, 91% 43 h P11FHppxSm, dePcFrHeaxsSe, ,9o8v%erPalFl O66S% Complete oxidation of bromide 15 ppm F- and chloride at 120 h PFOS groundwater treatment and PFBA, PFPeA, Decrease of PFBS produecletiovantoedf tsohxiocrtb-cyhparoinducts, PFSA >PsFhCoArtser-chain Literature - PFHxA, (83%), PFHxS (92%), concentrations after treatment, (13) Electrochemical, Concentrated PPFFHOpAA,, 18 h 0.02-20 PFFTOSSA ((9660%%)).aPnFdB6A:2, inefficient defluorination, optimization needed BDD groundwater PFBS, ppm PFPeA, PFHxA and PFHxS, PFOS and PFHpA increased. 42% F- 6:2 FTSA 10 mM F- ratios of 98.2-49.1% for PFCAs, 81.4-63.2% UV-sulfite / Na2SO3, and 5 mM PFCAs, 10 ppm for diPFCAs, 0.71- Generation of shorter-chain MS of intermediates, monitored (16) hydrated NaHCO3 (pH PFSAs, 48 h (relative to 33.4% for telomeric PFAS, generation of H- diPFCAs, PFOA) PFCAs, 0.94-57.0% for substituted PFAS DHEH, H/F exchange idnetegrrmadeadtiiaotneso,f DalFteTrncaatlecu/plarotipoonsseodf - electrons 9.5, adjusted by 1 M FTCAs PFSAs, smaller-chain BDE of intermediates NaOH) PFAS generated during degradation Aqueous. Ox: Oxidationreduction- K2S2O8 at pH 12, Red: PFCAs, 40 min- 207-10 97-103% F- except for n = 7, 8 fluorotelomers (53) oxidation (basic 10 mM of PFSAs, 24 h per ppm (85-89%), n = 4 PFSA Complicated treatment train persulfate Na2SO3 and 5 FTCAs, step (relative to (94%), and n = 4 FTSA oxidation, UVsulfite reduction) mM of NaHCO3 at FTSAs PFOA) (93%) pH 12. Literature, study of SO4- radical vs OH radical, characterization of Dpreotapiolesdalm, seecehapnaipsemr sintoteicrhmioemdieattrey doifsrtreibaucttaionnt,s consumed, DFT calculations of BDE of intermediates Energy consumption, the formation of toxic by-products, electrode issues such as mass transfer and fouling, and the lack of cost-effective and scalable electrode materials. (51, 52) - (15, 17) Hydrated electron processes can require extreme operating conditions, such as high temperature, high reductant dosage, and high solution pH. Needs testing in complex matrices. (20) - 79 pH 3.0-3.1, K2S2O8 (6.4- (18) Persulfate-UV 50.0 mM), PFOA aqueous solution (22) UV photolysis aqueous PFOA disappearance of PFOA after 4 h, production of 12 h 559 ppm disapFp- eaaftreerdP; F73O.A8% F- FormationPoFf CshAosrter-chains plus shorter-chain PFCAs 72 h 559 ppm 34% F-, fsohromretedr PFCAs Low defluorination DHEH DHEH "Generally, higher doses of persulfate, high temperature, or creating extreme pH Observations and literature Figure 2 - conditions are necessary to achieve an effective degradation of PFOA"; not effective for PFOS (20) 18O experiments Table 1 Entry 2 - P>2F2O0Andmoe(2s0n)ot absorb at wavelengths Proposed catalyst aqueous, 88% F-, suppressed Catalyst needs to be coordination and UV studies of catalyst under UV, tungstic 6.68 mM PFOA 24 h 559 ppm shorter-chain PFCA separated from reaction reoxidation steps, anaerobic conditions, 18O - - - (22) heteropolyacid tungstic generation compared to mixture proposed photo-Kolbe experiments polyacid direct photolysis decarboxylation cleavage, hydrolysis downstream aqueous, Direct photolysis leading to FeCl36H2O perfluoroalkyl radical, hydrolysis to shorter-chain (20 M), PFOA 72 h 15 ppm 100% F-, shorter Interference from matrix PFCA; Fe3+ complex with Literature, none Figure 1 - - (19) VUV-Fe various PFCAs formed constituents PFOA leading to PFOA additives radical, hydrolysis to tested shorter-chain PFCA Thermal (54) treatment of AC in N2 gas stream Activated carbon PFOA, PFHxA, PFOS 10 min 10 mg PFAS/g ~27-76% F- at 700 C, ~80% F- at 1000 C. Volatile organic fluorine found at 800-900 C. PFAS destroyed on surface of GAC at 700 C and destroyed in gas phase at 1000 C but in equilibrium with volatilizing at temperatures between 700- 1000 C, which gives incomplete destruction. Fluorine mass balance difficult to quantify; error is 20-30%. None N/A F2ig, u3r,e4s (55) - PFAS Thermal degradation of Thermal adsorbed to 7 PFCAs, 3 10 PFAS from 150-600 C (56) treatment of granulated activated PFSAs, C/min not for PFOA, 450-600 C ramp, 30 specified for PFOS; 80-90% F- High temperature Radicalmaencdhaalnkiesnme-based OrganofluToDri-nPeysrp-eGciCes-MidSentified by Figure 4 - - GAC carbon with HFPO-DA min hold for PFOA and PFOS at surface water temperatures 700 C 8 h, 350 Low concentrations of Nucleophilic hydroxide (23) Hydrothermal 1-5 M NaOH, PFOS C, 2- 50 ppm PFHpA, PFHxA and High temperature, pressure substitution of sulfonic acid Observation of shorter-chain Figure 2 (57) - Alkaline aqueous 16.5 PFPeA, 80-90% F- head group, subsequent intermediates, literature MPa DHEH DFT calculations of activation This Basic polar 8:1 24 h, 36,800 80-100 F-, TFA, Detailed mechanism energies, explanation of byproducts, aprotic solvent- DMSO:H2O, PFCAs 120 C ppm formate formed Organic solvent proposal, see paper NMR of intermediates, explanation of - - - Study assisted 2.67 M NaOH chain-length patterns, monitored degradation of intermediates Summary of emerging PFAS degradation methods and their major drawbacks. DHEH = decarboxylation-hydroxylation-elimination- hydrolysis (16). 80 Table S2. Summary of kinetic fitting parameters for degradation of PFOA at various temperatures. C a b c k adjusted trial R2 replicates 80 0.07476 2.90 x 105 0.02057 3.45 x 10-6 0.9466 single run 90 0.06934 8.62 x 104 0.01227 1.16 x 10-5 0.9842 duplicate 100 0.07908 3.82 x 104 0.00953 2.62x 10-5 0.9813 triplicate 120 0.08268 6.32 x 103 0.00449 1.58 x 10-4 0.9949 triplicate Kinetic fitting parameters for PFOA degradation at different temperatures (Figures S25-S28) as fitted to the equation y = ae-x/b + c in MATLAB using the Curve Fitting application. Table S3. Defluorination of various PFAS substrates under varying conditions. Compound 2 1 2 1 2 3 PFOS 1 1 1 controlc Solvent DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMAcb sulfolaneb water DMSO Temp (C) 40 40 120 120 40 40 120 120 120 120 120 Time 25 min 25 min 5 min 5 min 48 h 48 h 150 h 44 h 44 h 44 h 24 h F IC%a 4% n.d. 11% n.d. 57% 70% 0.3% 31% 38% 0.1% 0.2% Defluorination of various PFAS substrates under varying conditions, as measured by fluoride ion concentrations detected by ion chromatography. Perfluoro-1H-heptane (2) gives greater fluoride recovery than PFOA at the same times and temperatures, suggesting that decarboxylation is the rate-limiting step in this degradation. Even at low temperatures, 2 and perfluoro-1-heptene (3) both give relatively efficient defluorination (>50%). PFOS does not react under these conditions, and PFOA (1) does not defluorinate in pure water, only in polar aprotic solvents such as dimethylacetaminde (DMAc) or sulfolane. Control experiments run without PFOA show that the polytetrafluoroethylene reactor does not release fluoride into the reaction. a n.d. = not detected. b Using standard conditions for DMSO; not optimized for other solvents. 100% degradation of PFOA as all 19F NMR peaks disappeared. c Percent calculated relative to a 1 mmol PFOA degradation reaction; average of triplicate reactions. 82 Table S4. Distribution of carbonaceous byproducts of the PFOA degradation reaction, as measured by quantitative 13C NMR spectroscopy of the isolated reaction precipitate dissolved in D2O. Compound Mol% C relative to PFOA Mol/Mol PFOA Formatea 31.1 4.0 2.5 0.3 Carbonate 25.7 3.1 2.1 0.3 Oxalate 17.8 3.0 0.7 0.1 Glycolate Trifluoroacetateb Tartronatec 15.0 1.4 8.0 1.0 4.3 1.1 0.6 0.1c 0.32 0.04 0.2 0.1c Unidentified Total 4.9 2.4 106.7 8.3 0.4 0.2c 8.5 0.7d Unless noted, all errors reported as standard deviation of triplicate measurements. a Calculated by adding the formate in the reaction solvent, as measured by 1H NMR, to the formate in the reaction precipitate, as measured by 13C NMR. b Calculated via 19F NMR spectroscopy. c Error estimated as 0.1 based on the signal-to-noise of NMR resonances for low-concentration species. Errors for other products are given as the standard deviation of triplicate measurements. d Calculated as mols of carbon per mol of PFOA; i.e., accounting for compounds that have multiple carbons integrated in the analysis. 83 Data S1. XYZ Coordinates of Optimized DFT Structures and Corresponding Energies PFPeA E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1239.739617 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.022082 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.07736 a.u. G = E(DMSO) + Gcorr = -1239.717535 a.u. H = E(DMSO) + Hcorr = -1239.662257 a.u. C -2.84528300 -0.33932800 -0.18533300 C -1.55377900 0.39824300 0.31645700 F -1.54328100 0.49209200 1.66984500 O -3.49607300 0.26394200 -1.04186500 O -3.00368900 -1.43908200 0.36043000 F -1.45781900 1.66187500 -0.16328500 C -0.26921600 -0.34000300 -0.10458000 C 1.00501600 0.53627100 -0.05233700 C 2.31519100 -0.28067500 -0.03356500 F -0.07098200 -1.40637200 0.68731600 F -0.40887000 -0.77302200 -1.37142200 F 0.99094100 1.29891200 1.05060000 F 1.04349500 1.33001600 -1.12981000 F 2.50194900 -0.84839800 1.14819900 F 2.28377300 -1.22281200 -0.96805300 F 3.33707600 0.52927400 -0.27809800 Formate E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -189.762029 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.01005 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.038226 a.u. G = E(DMSO) + Gcorr = -189.751979 a.u. H = E(DMSO) + Hcorr = -189.723803 a.u. C 0.13093100 0.40154300 0.00004400 H 0.11314100 1.49760800 0.00042000 O 1.12633900 -0.26600400 -0.00005000 O -1.10704000 -0.08963400 -0.00014700 H -1.05312400 -1.06176500 0.00089000 GenX E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -2028.356103 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.051716 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.126659 a.u. G = E(DMSO) + Gcorr = -2028.304387 a.u. H = E(DMSO) + Hcorr = -2028.229444 a.u. 84 C -4.44504000 0.10771900 -0.28358800 C -3.14109700 -0.51613800 0.26092700 C -1.88388600 0.33284700 -0.05068300 C -0.57724800 -0.49189500 0.06187600 C 0.68547400 0.38509600 0.23210000 F -4.50247900 1.39310600 0.03902600 F -4.50683600 -0.01506400 -1.59956600 F -5.48057000 -0.51918300 0.25314100 F -3.00816500 -1.73291400 -0.28124500 F -3.26176600 -0.63704300 1.58589100 F -1.98057500 0.81600900 -1.29620000 F -1.84742800 1.35907700 0.80758600 F -0.45118500 -1.22633500 -1.04767500 F -0.66606800 -1.31056800 1.11980400 F 0.61880300 1.39789200 -0.64747500 F 0.68221600 0.92261000 1.45818400 O 1.75341600 -0.41586800 0.02571000 C 3.04182000 0.08556100 0.30904600 F 3.23093000 0.02801100 1.65605900 C 3.33429100 1.53433000 -0.25749500 O 3.31654200 2.42905700 0.58914200 O 3.53674400 1.54111200 -1.47685400 C 3.98433000 -0.97672400 -0.27165200 F 5.24753400 -0.57037900 -0.14451800 F 3.86216300 -2.12392800 0.40834700 F 3.74726400 -1.24786900 -1.54549100 1 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1953.114266 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.04928 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.121697 a.u. G = E(DMSO) + Gcorr= -1953.064986 a.u. H = E(DMSO) + Hcorr= -1952.992569 a.u. C 4.77319800 -0.14754100 -0.41572100 O 4.99396900 -1.35866900 -0.28532200 O 5.35808600 0.74082100 -1.03988300 C 3.49173700 0.31425800 0.36442500 C 2.21099300 -0.33527800 -0.19594800 C 0.90948200 0.41123100 0.19183200 C -0.35828100 -0.46657000 0.02986500 C -1.65660300 0.37668700 -0.05226800 C -2.92111200 -0.45864700 0.26857600 85 F 3.57861600 -0.01994200 1.67645900 F 3.30982400 1.65580900 0.31415800 F 2.10506900 -1.59966000 0.24397000 F 2.28513100 -0.35233000 -1.53930200 F 0.98404700 0.80155100 1.47151100 F 0.77205400 1.49476600 -0.58732000 F -0.45306600 -1.29427300 1.07907300 F -0.25547400 -1.19109700 -1.09131100 F -1.58565800 1.38571700 0.82494300 F -1.76838200 0.88147700 -1.28727300 F -3.02614600 -0.59122200 1.59351900 F -2.81202300 -1.67120500 -0.28803000 C -4.22286600 0.18965800 -0.25218100 F -5.26027900 -0.42597300 0.29344300 F -4.25502700 1.47277400 0.08319900 F -4.30487900 0.08027400 -1.56813100 5 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1691.303754 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.052111 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.119877 a.u. G = E(DMSO) + Gcorr = -1691.251643 a.u. H = E(DMSO) + Hcorr = -1691.183877 a.u. C 3.79738100 -0.15087900 -0.08148100 C 2.44682600 0.59677500 -0.14187700 C 1.23756200 -0.30397900 0.21000100 C -0.10203200 0.28641500 -0.29647900 C -1.34436800 -0.30439000 0.40558100 F 3.87583900 -0.85944500 1.03724900 F 3.92794500 -0.96050000 -1.11984900 F 4.78228400 0.73427000 -0.10222400 F 2.30069200 1.08363300 -1.38063100 F 2.49696600 1.61089100 0.72654100 F 1.41547700 -1.50785700 -0.35075000 F 1.19809100 -0.45108800 1.53952600 F -0.19056400 0.04419800 -1.60868200 F -0.09606100 1.61298900 -0.09771300 F -1.20350800 -1.64687500 0.46888800 F -1.36971600 0.13146100 1.68104800 O -2.42991200 0.07376500 -0.27711500 C -3.66695000 -0.48020200 0.16197400 H -3.60330300 -0.76457600 1.21183400 F -3.86427500 -1.61984700 -0.57082700 C -4.76725900 0.58770600 -0.07243200 86 O -5.58519100 0.35528900 -0.97191200 O -4.66766900 1.54962400 0.70818500 6 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1001.947909 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.012778 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.062475 a.u. G = E(DMSO) + Gcorr = -1001.935131 a.u. H = E(DMSO) + Hcorr = -1001.885434 a.u. C 2.24000800 0.06429800 -0.17808200 C 0.83658100 -0.40555800 0.34174700 F 0.79646600 -0.41137000 1.69851400 O 2.79163100 -0.70284100 -0.97085400 O 2.57408400 1.16054900 0.29012700 F 0.52841500 -1.66309200 -0.05805000 C -0.29768000 0.51570100 -0.14278700 C -1.70529400 -0.11073000 -0.07743900 F -0.33175000 1.63232300 0.59753900 F -0.08060200 0.85792800 -1.42693200 F -1.90693700 -0.67229000 1.10971900 F -1.86822600 -1.02774200 -1.02093000 F -2.62263500 0.83491600 -0.25706100 S3 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -351.821033 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.000198 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033629 a.u. G = E(DMSO) + Gcorr = -351.820835 a.u. H = E(DMSO) + Hcorr = -351.787404 a.u. C -0.55908200 -0.15439300 0.00010700 C 0.66984400 -0.72503400 0.00079700 O -1.69780600 -0.61418500 -0.00045400 F -0.47296400 1.26951500 0.00024900 F 1.81257500 0.06099200 -0.00052400 H 0.86137900 -1.78451700 0.00068200 S4 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -401.887993 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = -0.004819 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.028553 a.u. G = E(DMSO) + Gcorr= -401.892812 a.u. 87 H = E(DMSO) + Hcorr= -401.85944 a.u. C 0.18741500 -0.84810300 0.00000000 O 1.37337200 -1.19037000 0.00000000 O -0.86421500 -1.49564100 0.00000000 C 0.00000000 0.71577900 0.00000000 O 0.82212800 1.56185900 0.00000000 F -1.30830700 1.08746100 0.00000000 S5 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1089.171999 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.013571 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.065611 a.u. G = E(DMSO) + Gcorr = -1089.158428 a.u. H = E(DMSO) + Hcorr = -1089.106388 a.u. C 2.92762700 -0.46464300 -0.38160200 C 1.98371200 0.42757200 -0.07844400 C 0.63302400 0.27225600 0.54277300 C -0.47067800 -0.02507400 -0.49249000 F 2.52670000 -1.75334400 -0.00581600 F 2.19322300 1.73853600 -0.42822900 F 0.60875900 -0.73154600 1.44639500 F 0.26541700 1.40853900 1.19052700 F -0.19277200 -1.19371000 -1.09056600 F -0.46167100 0.94947000 -1.41858500 C -1.91233100 -0.12442300 0.04025700 F -2.01182900 -1.06635900 0.96819100 F -2.31352300 1.03096700 0.55148700 F -2.72187100 -0.43967800 -0.96706600 S6 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -252.545844 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.009188 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.040346 a.u. G = E(DMSO) + Gcorr= -252.536656 a.u. H = E(DMSO) + Hcorr= -252.505498 a.u. C 0.63748200 -0.30665700 -0.00002100 C -0.48555700 0.45585800 0.00000000 O 1.85350600 0.07602900 0.00001000 F -1.73141200 -0.18215500 0.00000500 88 H -0.57475300 1.53297300 -0.00001300 H 0.41785800 -1.39701900 0.00001200 S7 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -237.693767 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = -0.016377 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.010922 a.u. G = E(DMSO) + Gcorr = -237.710144 a.u. H = E(DMSO) + Hcorr = -237.682845 a.u. C 0.00000000 0.00000000 0.59047700 F 0.00000000 -1.02383600 -0.19682600 F 0.00000000 1.02383600 -0.19682600 S8 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -403.090969 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.018354 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.053756 a.u. G = E(DMSO) + Gcorr = -403.072615 a.u. H = E(DMSO) + Hcorr = -403.037213 a.u. C -0.64585300 -0.20205800 0.39857500 F -1.12899900 -1.11853300 -0.56843200 C 0.84299700 0.05474500 0.04981700 O 1.63777500 -0.86051000 0.30158900 O 1.04997300 1.17568600 -0.47033200 H -0.79035100 -0.70028300 1.35655000 O -1.37053300 0.94731000 0.32246600 H -0.76924700 1.55106700 -0.16079500 INT1 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1764.479498 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.036801 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.103691 a.u. G = E(DMSO) + Gcorr= -1764.442697 a.u. H = E(DMSO) + Hcorr= -1764.375807 a.u. C 4.20136300 -0.07233900 -0.00445300 C 2.83164800 0.42295900 0.43959700 C 1.56266200 -0.32894200 -0.04082800 C 0.25904600 0.50309200 0.07037800 C -1.02088600 -0.37158200 0.04869000 C -2.28678900 0.43862600 -0.32651600 F 4.20180200 0.13803900 -1.40261700 89 F 4.07114800 -1.48454600 0.08504900 F 2.69167500 1.71959800 0.05781800 F 2.78032500 0.38938100 1.79756900 F 1.69632200 -0.69296300 -1.32586500 F 1.39962300 -1.44348600 0.69838500 F 0.19948000 1.36368300 -0.95798200 F 0.26304700 1.19806300 1.21636300 F -0.87710200 -1.35619300 -0.84813800 F -1.19805000 -0.91422100 1.26125500 F -2.31609200 0.60691200 -1.65184500 F -2.25123800 1.63740100 0.26884200 C -3.59905800 -0.26008800 0.09090600 F -4.61837600 0.34692900 -0.49767100 F -3.57533800 -1.53125400 -0.28840900 F -3.76588300 -0.19849100 1.40206200 INT2 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1664.501639 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.036315 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.101983 a.u. G = E(DMSO) + Gcorr= -1664.465324 a.u. H = E(DMSO) + Hcorr= -1664.399656 a.u. C 2.79182500 -1.38547500 -0.15575400 C 2.45240100 -0.25186600 0.43257700 C 1.88800700 0.96251700 -0.22925700 C 0.40364500 1.23924400 0.12607100 F 2.56932700 -0.13964300 1.75793600 F 0.33995200 1.62953200 1.40445800 F -0.03546800 2.23586700 -0.65506900 F 3.25921700 -2.40255900 0.50943700 C -0.51469100 0.00787700 -0.05549400 F -0.33791600 -0.80537500 0.99625400 F -0.16178700 -0.64954300 -1.16842500 C -2.01171900 0.38408000 -0.16098700 F -2.29093800 1.35645800 0.71527300 F -2.25885700 0.82167300 -1.39836100 C -2.95589200 -0.80551200 0.12330600 F -2.97440500 -1.08755300 1.41557700 F -4.18115500 -0.48744800 -0.26365300 F -2.55174200 -1.87340600 -0.55231200 F 1.98624300 0.87591500 -1.56196100 F 2.69864900 -1.62796800 -1.42990800 F 2.56983000 2.05347400 0.17711400 90 INT3 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1740.492919 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.048745 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.116177 a.u. G = E(DMSO) + Gcorr= -1740.444174 a.u. H = E(DMSO) + Hcorr= -1740.376742 a.u. C 3.52727300 -0.71427400 -0.20976100 C 2.06967600 -0.60524100 0.00297300 C 1.54219700 0.75507400 -0.16253100 C 0.09162000 0.94877700 0.34132700 F 1.85754300 -0.97539300 1.36316300 F 0.05691800 0.95333000 1.68204300 F -0.33769600 2.15998900 -0.08081100 F 4.30247000 -0.06675200 0.75994100 C -0.92825700 -0.09503000 -0.16654900 F -0.79411900 -1.23216900 0.52993200 F -0.71603300 -0.34865700 -1.46469300 C -2.39656900 0.38613500 -0.02637800 F -2.56591400 1.03095800 1.13565700 F -2.68346300 1.22032900 -1.03198500 C -3.41809800 -0.77279600 -0.07349600 F -3.40348400 -1.45887800 1.05836300 F -4.63308300 -0.27254500 -0.24950200 F -3.13951100 -1.58930800 -1.08160600 F 1.55702200 1.14383100 -1.46383700 F 3.93091700 -2.02442400 -0.02957000 O 3.91283500 -0.27123000 -1.42531500 H 4.88238600 -0.26461800 -1.45210500 F 2.22264400 1.79508700 0.49747400 INT4 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1640.497449 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047743 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.114179 a.u. G = E(DMSO) + Gcorr = -1640.449706 a.u. H = E(DMSO) + Hcorr = -1640.38327 a.u. C 2.85944600 -1.34885300 -0.15502800 C 2.44201300 -0.23105600 0.42926800 C 1.87396400 0.97858800 -0.22393300 C 0.38627500 1.24064500 0.12945200 F 2.47974300 -0.13723100 1.76898500 91 F 0.31163100 1.61993900 1.41129500 F -0.06193500 2.24174400 -0.64344100 F 3.25806300 -2.35025900 0.61297600 C -0.52391900 0.00597900 -0.06704000 F -0.34021800 -0.82302000 0.97151800 F -0.17427900 -0.63238200 -1.19168900 C -2.02445300 0.37311700 -0.16083300 F -2.31043800 1.32715800 0.73340200 F -2.28020700 0.83162800 -1.38931600 C -2.95925300 -0.82838400 0.10415800 F -2.97465900 -1.13273500 1.39150600 F -4.18761300 -0.51281000 -0.27576200 F -2.54915400 -1.88238200 -0.58964100 F 1.97355700 0.91194700 -1.55764500 O 2.96269000 -1.56782300 -1.45017900 H 2.84212300 -2.51618500 -1.63477500 F 2.53683300 2.08490700 0.19113900 INT5 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1640.061417 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.035336 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.100773 a.u. G = E(DMSO) + Gcorr = -1640.026081 a.u. H = E(DMSO) + Hcorr = -1639.960644 a.u. C 2.86156400 -1.39937900 -0.32407400 C 2.51872700 -0.25233000 0.35189000 C 1.91802900 0.94832900 -0.21894500 C 0.43741200 1.20964100 0.16452900 F 2.45242400 -0.25473500 1.72901700 F 0.36361500 1.53120700 1.46573500 F -0.03308700 2.25363400 -0.54970400 F 3.20911300 -2.40409200 0.59355000 C -0.49104300 -0.00232300 -0.07900800 F -0.32299800 -0.88490700 0.91847800 F -0.17325800 -0.59672000 -1.23580400 C -1.98807500 0.38873300 -0.14047700 F -2.26011300 1.30454000 0.79849400 F -2.25505800 0.90602100 -1.34439000 C -2.93823100 -0.80952600 0.08020600 F -2.95393500 -1.16606400 1.35468300 F -4.16521800 -0.46100000 -0.27894300 F -2.55115900 -1.84256600 -0.65686700 F 1.98220600 0.95701400 -1.56346300 92 O 2.93798500 -1.68812300 -1.49814500 F 2.55033700 2.10279100 0.21148400 INT6 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1540.049441 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.034397 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.098281 a.u. G = E(DMSO) + Gcorr = -1540.015044 a.u. H = E(DMSO) + Hcorr = -1539.95116 a.u. C 4.00480900 -0.38827400 -0.39493400 C 2.66942000 -0.31640900 0.23667900 C 1.80938000 0.67256200 0.02369800 C 0.43217600 0.76996300 0.64636300 F 2.35681600 -1.31945300 1.04395800 F 0.43465400 0.25407000 1.88055900 F 0.07358700 2.06185400 0.71307600 O 4.48470800 0.38359600 -1.14442700 F 4.64764600 -1.48819500 -0.00208300 C -0.62170800 0.02405000 -0.20443800 F -0.42409400 -1.29220600 -0.05025200 F -0.42197200 0.34393200 -1.49026400 C -2.08275400 0.37803600 0.16290200 F -2.20745700 0.47562600 1.49153800 F -2.39035700 1.55392000 -0.39183300 C -3.10126600 -0.66905500 -0.33975100 F -3.03953400 -1.76741900 0.39504700 F -4.32182900 -0.16392900 -0.25397200 F -2.84747000 -0.97512200 -1.60559300 F 2.08023300 1.66203100 -0.79992700 INT7 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1616.058051 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.048909 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.113731 a.u. G = E(DMSO) + Gcorr = -1616.009142 a.u. H = E(DMSO) + Hcorr = -1615.94432 a.u. C 3.64735000 -0.76575300 0.33815800 C 2.43300500 -0.55062700 -0.23628300 C 1.83826900 0.78746900 -0.37380200 C 0.41263400 0.94973400 0.22607100 F 1.76861200 -1.56303700 -0.87608100 93 F 0.50958400 0.88539900 1.56751200 F -0.05331800 2.17918000 -0.09195400 O 4.41458300 0.03812800 0.88481000 F 4.05143900 -2.07921800 0.29957000 C -0.67056900 -0.07243300 -0.19122900 F -0.48787800 -1.21029900 0.49981800 F -0.59608600 -0.34402800 -1.50002700 C -2.10954400 0.43160000 0.09249300 F -2.15635000 1.06735500 1.27048400 F -2.47634800 1.27898800 -0.87577900 C -3.15313500 -0.70778300 0.13726900 F -3.04344300 -1.40256100 1.25876200 F -4.36930900 -0.18286100 0.08233200 F -2.99049300 -1.52236000 -0.89734500 F 1.63437400 1.08945700 -1.74006200 O 2.59354100 1.76810100 0.18396500 H 3.42988300 1.35278100 0.51864300 INT8 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1515.607827 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033937 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.097523 a.u. G = E(DMSO) + Gcorr = -1515.57389 a.u. H = E(DMSO) + Hcorr = -1515.510304 a.u. C 3.95805700 -0.46657700 -0.32059100 C 2.65602400 -0.25512500 0.18137600 C 1.87832600 0.87068800 -0.09976600 C 0.45616400 0.90512600 0.54274300 F 2.14775700 -1.23574100 0.99186300 F 0.45882500 0.52088200 1.83728600 F -0.00824200 2.17102400 0.50454400 O 4.64975200 0.19516300 -1.03768500 F 4.46636700 -1.67092600 0.13406500 C -0.57073000 0.04207400 -0.21899600 F -0.37154700 -1.25396700 0.06601900 F -0.38928000 0.21895700 -1.53802100 C -2.04479100 0.39409700 0.10126600 F -2.18480800 0.65026000 1.40859100 F -2.39779200 1.48059100 -0.59509000 C -3.03142600 -0.73643800 -0.26365600 F -2.94235500 -1.73577600 0.60005800 F -4.26920000 -0.26202400 -0.23597500 F -2.77249300 -1.18971900 -1.48388600 94 O 2.16964300 1.83419700 -0.80473200 INT9 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.521889 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046575 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.112254 a.u. G = E(DMSO) + Gcorr = -1591.475314 a.u. H = E(DMSO) + Hcorr = -1591.409635 a.u. C -3.49910600 -0.98126500 -0.08961200 C -3.05978200 0.30120300 -0.07538800 C -1.70528300 0.90032900 0.28256400 C -0.56218700 -0.14080600 0.03239500 F -0.70825000 -0.86140200 -1.11139100 O -2.97545200 -2.08975900 -0.00571300 O -1.60777100 1.42784000 1.47489800 O -1.43219100 1.90002700 -0.77486900 H -1.15792200 2.65593800 -0.24174300 F -4.93818200 -1.02175400 -0.26501000 F -0.49783200 -1.03411200 1.05402000 F -4.02234100 1.30357600 -0.12479600 C 0.85926400 0.48586500 -0.09306900 C 1.98805700 -0.49665800 0.31067000 C 3.38840400 -0.07823000 -0.19295000 F 1.10247500 0.83244800 -1.37513100 F 1.01958700 1.58087800 0.66196500 F 1.75183500 -1.71966800 -0.18989300 F 2.05848500 -0.57629600 1.64683700 F 3.50746100 -0.28956800 -1.49576000 F 3.62252700 1.20324600 0.05958400 F 4.30701600 -0.80661900 0.43286000 INT10 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1592.038358 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.059893 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.126051 a.u. G = E(DMSO) + Gcorr = -1591.978465 a.u. H = E(DMSO) + Hcorr = -1591.912307 a.u. C 3.48130100 0.99458200 -0.13578200 C 3.00824300 -0.35075600 -0.59820500 C 1.72444400 -0.80230100 0.21959300 C 0.52915900 0.12952300 -0.19205800 95 F 0.58400000 0.49874700 -1.50129400 O 3.09937700 2.04999800 -0.50420200 O 1.91682200 -0.84283300 1.49071700 O 1.38583200 -2.07010200 -0.39720900 H 1.40928000 -2.67833600 0.35233300 F 4.43040300 0.91400100 0.81209700 F 0.56567700 1.27261200 0.53350000 F 3.98507900 -1.28644500 -0.34073500 H 2.83683000 -0.31502200 -1.67296300 C -0.87200600 -0.49706100 0.01613700 C -1.98761700 0.56519800 0.18583100 C -3.41139300 0.00955200 -0.04160800 F -1.20317200 -1.24676800 -1.05129200 F -0.89973000 -1.27543500 1.10606500 F -1.81155000 1.56523500 -0.69099600 F -1.94669100 1.06053200 1.42923200 F -3.63712600 -0.20149200 -1.32963800 F -3.58036900 -1.12824400 0.62018900 F -4.29709300 0.89441600 0.39984300 INT11 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1764.996384 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.051569 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.118723 a.u. G = E(DMSO) + Gcorr = -1764.944815 a.u. H = E(DMSO) + Hcorr = -1764.877661 a.u. C -1.51673500 -0.33739500 -0.03875400 C -2.76990500 0.43779100 0.43655200 C -4.09524700 -0.14403600 -0.06858200 F -1.68237200 -0.70893500 -1.31414400 F -1.37555900 -1.43508900 0.71784500 F -4.05171300 -1.48556600 0.08003200 F -2.67637700 1.71291400 0.02285000 F -2.78741500 0.41926700 1.77824700 H -4.93293500 0.27114000 0.49236000 F -4.23113900 0.13081400 -1.37909000 C -0.22048400 0.50544200 0.06410700 C 1.05809800 -0.37147700 0.05357600 C 2.32261200 0.43777500 -0.32761100 C 3.63520100 -0.25866200 0.09280800 F 3.61025100 -1.53044400 -0.28394200 F 3.79956100 -0.19390000 1.40378800 F 2.34826500 0.59868500 -1.65318900 F 2.28159500 1.63868900 0.26229500 96 F 0.90624300 -1.36088100 -0.83571100 F 1.22794300 -0.90333600 1.27012900 F -0.17172200 1.35260300 -0.97176300 F -0.24533100 1.20790600 1.20333900 F 4.65351500 0.34751900 -0.49678800 INT12 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1740.461376 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.049246 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.116617 a.u. G = E(DMSO) + Gcorr = -1740.41213 a.u. H = E(DMSO) + Hcorr = -1740.344759 a.u. C -2.45051000 -1.49293600 0.64239600 C -2.69791000 -0.17170500 -0.08817000 C -1.74766200 0.98527000 0.29494300 C -0.29624200 1.07772500 -0.26549600 F -2.54816700 -0.28397500 -1.48191300 F -0.33851700 1.25944700 -1.58948700 F 0.20697000 2.20428300 0.28848600 F -3.59937000 -2.25089600 0.21048400 C 0.70922000 -0.06462600 0.03385800 F 0.65926400 -0.97040300 -0.94953700 F 0.41114100 -0.63988900 1.20338100 C 2.17112700 0.44500600 0.10819600 F 2.39711300 1.30416900 -0.89532400 F 2.37194100 1.05995300 1.27689400 C 3.21459200 -0.69146500 -0.00943100 F 3.30229800 -1.12158700 -1.25788600 F 4.39886700 -0.22688700 0.36255300 F 2.88385900 -1.70569300 0.77848500 F -1.66308700 1.08847100 1.63229500 F -1.43232400 -2.11947400 -0.09756000 F -2.30406200 2.13518400 -0.15929600 O -3.95181500 0.29467500 0.18184100 H -4.51451300 -0.47533000 0.35333000 INT13 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1616.029125 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.045918 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.112973 a.u. G = E(DMSO) + Gcorr = -1615.983207 a.u. H = E(DMSO) + Hcorr = -1615.916152 a.u. 97 C -2.45073400 -0.12081400 0.31984700 C -1.58218700 0.77231300 -0.13154800 C -0.19357100 0.98584300 0.41141000 C 0.84214900 0.02097000 -0.20800200 C 2.23404800 0.05799600 0.46848600 F -1.83767800 1.57504300 -1.17010700 F -0.14231100 0.81898400 1.74754800 F 0.19931100 2.24290800 0.13022900 F 0.37814900 -1.23203100 -0.10764700 F 0.97187600 0.32778900 -1.50914400 F 2.17772300 -0.64991500 1.60207600 F 2.58121600 1.31721300 0.76081500 F -2.05810300 -0.89316200 1.33682100 C -3.90122700 -0.38898400 -0.06953500 O -4.72977700 -0.34775100 0.85789400 C 3.35164600 -0.54309500 -0.41158600 F 3.65443000 0.27902900 -1.40413900 F 4.43343900 -0.73208300 0.33003100 F 2.96327600 -1.70798800 -0.91332800 F -3.69294800 -1.86259000 -0.57469400 O -4.18535700 0.28386500 -1.24903600 H -5.13509800 0.45694700 -1.20144100 INT14 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1515.589855 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033678 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.097949 a.u. G = E(DMSO) + Gcorr = -1515.556177 a.u. H = E(DMSO) + Hcorr = -1515.491906 a.u. C 2.70501900 0.32680800 0.21894000 C 1.86495000 -0.67348700 -0.02175500 C 0.49724100 -0.83722700 0.59441800 C -0.58218500 -0.05553300 -0.19099800 C -2.00636300 -0.10933300 0.40479000 F 2.12763200 -1.64702200 -0.89470900 F 0.46933400 -0.41743900 1.87202500 F 0.15925800 -2.14117900 0.57481200 F -0.21067900 1.23180600 -0.24390900 F -0.61321700 -0.55246100 -1.43829600 F -2.01421700 0.55781800 1.56551600 F -2.36353700 -1.38068500 0.62357300 F 2.28474100 1.25984900 1.08355700 C 4.10381500 0.56548800 -0.37622600 O 4.62862800 1.62794900 -0.01492100 98 O 4.51261200 -0.32880100 -1.13079700 C -3.09752800 0.52065400 -0.48954100 F -3.24903700 -0.17003400 -1.60864300 F -4.24414700 0.50401200 0.17792800 F -2.79497800 1.77562600 -0.78652300 INT15 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.516658 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.04802 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.11318 a.u. G = E(DMSO) + Gcorr= -1591.468638 a.u. H = E(DMSO) + Hcorr= -1591.403478 a.u. C 3.83428900 -0.87650500 -0.34675100 C 2.37243400 -0.74130000 -0.07462200 C 1.86724300 0.66121100 -0.07691400 C 0.40616100 0.80054100 0.44620700 F 2.06121400 -1.22400600 1.25499200 F 0.33695700 0.64685800 1.77997300 F -0.00386400 2.08003100 0.19179900 O 4.50635500 -1.67151400 0.36734900 C -0.66280600 -0.12503700 -0.17894500 F -0.59898600 -1.34222000 0.38242900 F -0.48107800 -0.24818300 -1.50100200 C -2.10807400 0.40754600 0.02168900 F -2.25937100 0.91868500 1.25138300 F -2.35540500 1.36678000 -0.87937000 C -3.18962500 -0.68033000 -0.15892900 F -3.20859500 -1.50792400 0.87450400 F -4.37775500 -0.09590400 -0.25090400 F -2.96822500 -1.37395700 -1.26804500 F 1.77606200 1.16297600 -1.37565000 O 2.62492100 1.57608700 0.65434400 H 2.24285500 2.46222500 0.56061900 O 4.28757700 -0.22797500 -1.33319400 INT16 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1491.099371 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033874 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.097175 a.u. G = E(DMSO) + Gcorr= -1491.065497 a.u. H = E(DMSO) + Hcorr= -1491.002196 a.u. 99 C 4.07695500 -0.62105900 -0.28988800 C 2.70061500 -0.25745800 0.16763400 C 1.93467000 0.85074100 -0.10257100 C 0.51044600 0.87069600 0.54916600 F 2.12065100 -1.21294100 0.99838000 F 0.47568300 0.50195200 1.85605700 F 0.02231200 2.13759800 0.51425700 O 4.53608100 -1.70783500 0.14945400 C -0.53099500 0.01450600 -0.20283200 F -0.38077800 -1.28446400 0.10718100 F -0.34303300 0.15205600 -1.52764700 C -2.00353700 0.40204700 0.08673300 F -2.16715700 0.68936300 1.38599400 F -2.33176900 1.47875500 -0.63930100 C -3.00944300 -0.71519600 -0.26643500 F -2.95893200 -1.69609000 0.62227900 F -4.23831900 -0.21351500 -0.26811800 F -2.74778700 -1.20598500 -1.47172600 O 2.16714600 1.86021100 -0.81321900 O 4.65551000 0.17434500 -1.06711500 INT17 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1491.597622 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047996 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.111136 a.u. G = E(DMSO) + Gcorr= -1491.549626 a.u. H = E(DMSO) + Hcorr= -1491.486486 a.u. C 3.11728700 -1.24329800 0.08415600 C 3.17682300 0.31914000 0.12049000 C 1.86249500 0.84142400 -0.38478800 C 0.64345900 0.82330600 0.57506500 F 4.18035100 0.82985100 -0.66832700 F 0.99691500 0.61377700 1.84892200 F 0.11533500 2.07268400 0.52115700 O 4.11174100 -1.82808200 -0.34342200 C -0.47758900 -0.20000300 0.17674800 F -0.60014100 -1.13317200 1.12431900 F -0.17720900 -0.78482900 -0.99101800 C -1.86811900 0.45574300 0.00538000 F -2.20076300 1.10402300 1.13117700 F -1.83199900 1.31717000 -1.01961400 C -3.01727300 -0.53726200 -0.28479800 F -3.21792200 -1.34695500 0.74360200 100 F -4.12630000 0.16436600 -0.49067800 F -2.76762000 -1.25933500 -1.36663300 O 1.69389900 1.30412100 -1.47601000 O 2.03128500 -1.67479800 0.51931700 H 3.34627600 0.63755900 1.15122900 INT18 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1567.555407 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.061602 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.126622 a.u. G = E(DMSO) + Gcorr= -1567.493805 a.u. H = E(DMSO) + Hcorr= -1567.428785 a.u. C 3.81439100 -0.94764600 -0.15240000 C 2.31482300 -0.69690100 0.13811500 C 1.84972100 0.68699800 -0.37006200 C 0.38532700 0.97656300 0.13412300 F 0.29152400 1.17627700 1.47721200 F -0.06329000 2.12621300 -0.44212400 O 4.10325600 -2.00787400 -0.73241000 C -0.67336400 -0.10495100 -0.18127700 F -0.55741700 -1.10934900 0.71592400 F -0.51324300 -0.63213600 -1.40258600 C -2.13366600 0.41441500 -0.11357800 F -2.29829200 1.26628900 0.90829400 F -2.42550900 1.05109500 -1.25644900 C -3.17790200 -0.70901800 0.06641700 F -3.15375500 -1.18184500 1.30403300 F -4.38926200 -0.21906500 -0.17045000 F -2.94874000 -1.70320700 -0.78215100 O 1.91384500 0.74600400 -1.67192100 O 4.60865300 -0.06783900 0.27264600 O 2.59068000 1.69746100 0.35261000 H 3.48880600 1.31107100 0.41157700 F 2.14543400 -0.82823100 1.53835500 H 1.71669400 -1.48421700 -0.31751200 INT19 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1467.574059 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.060697 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.122871 a.u. G = E(DMSO) + Gcorr= -1467.513362 a.u. H = E(DMSO) + Hcorr= -1467.451188 a.u. 101 C -4.39158000 -0.01878300 -0.02004200 C -3.03645800 0.64647400 -0.26192000 C -1.83745500 -0.18326200 -0.04718200 C -0.54325300 0.47127700 0.38401800 F -0.50852300 0.58127800 1.72790500 O -5.36051100 0.73143200 0.10984000 O -2.23872400 0.12412500 -1.34987700 O -1.91660400 -1.46256200 0.37357700 H -2.92601900 -1.64612600 0.28527700 F -0.44744100 1.71315900 -0.13369000 H -2.99997700 1.72462200 -0.15929000 C 0.71061900 -0.31905000 -0.05651800 C 2.00095200 0.53592500 -0.05911600 C 3.29372100 -0.30888100 -0.04534600 F 0.89725600 -1.36054300 0.76769900 F 0.52051100 -0.78361500 -1.30033800 F 2.02213400 1.33005900 1.02040100 F 2.02346900 1.29479900 -1.16032500 F 3.49696900 -0.83849600 1.15065300 F 3.21440400 -1.28185600 -0.94452900 F 4.32414000 0.46922100 -0.34504900 O -4.37660600 -1.28508800 0.04972300 INT20 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1467.587186 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.059994 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.12368 a.u. G = E(DMSO) + Gcorr= -1467.527192 a.u. H = E(DMSO) + Hcorr= -1467.463506 a.u. C 3.07308400 1.31353300 0.06015200 C 3.13751600 -0.23789700 0.38194200 C 1.93955000 -0.86213600 -0.27754300 C 0.58833600 -0.86428400 0.48459700 F 0.64590600 -0.22955200 1.66580000 O 4.06225000 1.71560200 -0.57940100 O 4.31710100 -0.78627000 -0.10788700 O 1.93734400 -1.38904700 -1.35557300 F 0.26903400 -2.15476000 0.74008100 H 3.05658500 -0.35238300 1.46627700 C -0.56365500 -0.26529700 -0.35870400 C -1.77721600 0.16220200 0.49862400 C -3.07280900 0.35083100 -0.32163600 F -0.13003700 0.80231800 -1.03617900 102 F -0.98109200 -1.18766700 -1.24278300 F -1.50482900 1.32280700 1.10223600 F -2.02045000 -0.77253200 1.42917900 F -2.82990700 1.07342300 -1.40726500 F -3.57452300 -0.81983000 -0.68301000 F -3.96864600 0.98347200 0.42342400 O 2.07227200 1.91441500 0.46328200 H 4.73373000 -0.02605300 -0.55759000 INT21 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.987059 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.048508 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10651 a.u. G = E(DMSO) + Gcorr= -1278.938551 a.u. H = E(DMSO) + Hcorr= -1278.880549 a.u. C 3.29679600 -0.61603300 0.63189400 C 2.54643000 0.12407900 -0.21727900 C 1.21746200 0.62619000 0.29362800 F 1.14903600 0.64286400 1.65272400 F 0.97665900 1.90197500 -0.12474200 C 0.00739800 -0.21442900 -0.17304500 F -0.01757600 -1.36086700 0.53669800 F 0.12849300 -0.53408600 -1.46916000 C -1.36244100 0.48873000 -0.00513300 F -1.40690500 1.17209900 1.14732400 F -1.53942700 1.34437400 -1.02100600 C -2.56100600 -0.48346300 -0.00638500 F -2.61500900 -1.16605400 1.12761200 F -3.68529900 0.21004900 -0.13414500 F -2.46602600 -1.33349400 -1.02117500 O 2.86604200 0.39116600 -1.43682600 H 3.06887100 -0.86177000 1.65684800 O 4.48885200 -1.11380300 0.15207000 H 4.50863800 -0.79932400 -0.76804100 INT22 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.452041 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.034676 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.09191 a.u. G = E(DMSO) + Gcorr= -1278.417365 a.u. H = E(DMSO) + Hcorr= -1278.360131 a.u. 103 C -3.47200100 0.71588600 -0.34947000 C -2.63850400 -0.39147100 -0.33749100 C -1.37728800 -0.35013200 0.45943800 F -1.37019800 0.52615500 1.50664900 F -1.08699100 -1.58351900 1.03234100 C -0.09353300 -0.00449800 -0.34368100 F -0.06833500 1.32950100 -0.57047800 F -0.08748400 -0.61244600 -1.54201200 C 1.24562500 -0.38150700 0.33944700 F 1.20179600 -0.13898300 1.65894000 F 1.48448100 -1.68938900 0.15305900 C 2.46807800 0.38286100 -0.21132900 F 2.46431800 1.64346700 0.19918100 F 3.58322000 -0.19316100 0.22733600 F 2.47692800 0.36065000 -1.53885200 O -2.79462400 -1.51054000 -1.04549700 H -4.34094200 0.51627500 -1.02267500 O -3.43449000 1.87009200 0.23871200 INT23 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1178.525239 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.031733 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.089049 a.u. G = E(DMSO) + Gcorr= -1178.493506 a.u. H = E(DMSO) + Hcorr= -1178.43619 a.u. C -3.79077200 -0.02941600 0.25801200 C -2.42290900 -0.65695500 0.02963400 C -1.42795700 0.14533100 -0.46716400 F -1.65365700 1.48253600 -0.70183000 C -0.02043600 -0.20822400 -0.70884400 F 0.46123100 0.43659400 -1.81883800 F 0.14054400 -1.53342100 -0.90840900 C 0.93910800 0.18200000 0.44128300 F 0.74406000 1.47612400 0.75345000 F 0.63997900 -0.56757600 1.51522800 C 2.44809700 0.01362300 0.18292800 F 2.87402800 0.86949900 -0.73622800 F 3.11382800 0.25173500 1.31107800 F 2.72953000 -1.22086500 -0.21444500 O -2.38547100 -1.87871100 0.33370400 H -4.61336300 -0.72870500 0.01362500 O -4.01244600 1.04107700 0.76269900 104 INT24 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1078.514592 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.031303 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.086442 a.u. G = E(DMSO) + Gcorr= -1078.483289 a.u. H = E(DMSO) + Hcorr= -1078.42815 a.u. C -3.60886800 0.59723200 -0.15617100 C -2.55426600 -0.50593700 -0.02749800 C -1.17792000 -0.10845400 0.38064000 F -1.08161500 1.03217000 1.05837500 C -0.07952100 -0.80558400 0.11532900 F -0.12082900 -1.92242000 -0.58703500 C 1.32241600 -0.40559100 0.51655200 F 1.32840100 0.19606600 1.71474700 F 2.09292800 -1.50193400 0.57822200 C 1.98091500 0.56153800 -0.48373600 F 1.28756100 1.69060100 -0.54322500 F 3.21862300 0.83579000 -0.09968700 F 2.01499200 0.00854000 -1.68925600 O -2.85214700 -1.63480600 -0.30889000 H -4.64614600 0.23953900 -0.06005900 O -3.31172100 1.72379600 -0.42859600 INT25 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1154.485333 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.043074 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.101363 a.u. G = E(DMSO) + Gcorr= -1154.442259 a.u. H = E(DMSO) + Hcorr= -1154.38397 a.u. C -3.16714100 0.84937700 -0.01711700 C -2.40427600 -0.44176800 0.31226200 C -0.98563300 -0.39667500 -0.28877200 F -0.65545300 -1.35176900 -1.16505600 C -0.04925400 0.47975700 0.03988400 F -0.29276800 1.43552300 0.94831000 C 1.36505000 0.50825400 -0.45628600 F 1.45830100 0.10829200 -1.73872000 F 1.85514400 1.76247300 -0.37122400 C 2.31541700 -0.38771400 0.35369700 F 1.94693900 -1.65883200 0.24730100 F 3.56241100 -0.26980700 -0.08909000 105 F 2.28566600 -0.03749300 1.63538900 O -2.40556000 -0.62804300 1.60849500 H -4.16960000 0.84167600 0.45559300 O -2.76804200 1.80261500 -0.63553500 O -3.11999100 -1.46513500 -0.42290000 H -3.36880300 -2.08002400 0.27971900 INT26 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1153.957796 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033008 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.087809 a.u. G = E(DMSO) + Gcorr= -1153.924788 a.u. H = E(DMSO) + Hcorr= -1153.869987 a.u. C -3.14643200 0.81602800 0.22506300 C -2.46337900 -0.54939300 0.27118500 C -1.02492500 -0.43718100 -0.31853800 F -0.64428700 -1.48333600 -1.07481700 C -0.08362300 0.47442300 -0.09113300 F -0.31766700 1.51042300 0.74779000 C 1.33949400 0.44780900 -0.53588500 F 1.49321200 -0.12891900 -1.74645400 F 1.83271500 1.70824400 -0.61567900 C 2.27350800 -0.30922000 0.42123900 F 1.93310300 -1.59218000 0.47735400 F 3.54001100 -0.22994600 0.01839300 F 2.19062000 0.20836300 1.64405000 O -2.30819100 -0.98047600 1.54036300 H -4.06690200 0.79156200 0.85296500 O -2.88557800 1.80644300 -0.42971600 O -3.25002100 -1.24849100 -0.57818100 INT27 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.544297 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047579 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.11277 a.u. G = E(DMSO) + Gcorr= -1591.496718 a.u. H = E(DMSO) + Hcorr= -1591.431527 a.u. C -4.16901800 0.53002200 0.00554600 C -2.86342700 -0.30610500 0.28145800 C -1.59549500 0.49333300 0.11952000 C -0.39749600 -0.35389400 -0.01816200 106 F -2.95170600 -0.69546600 1.64800800 F -0.36135500 -1.28976800 0.96902500 F -0.24789000 -1.07129000 -1.21391800 O -4.32144600 1.59191000 0.61788900 C 0.93509900 0.42862700 0.08749100 F 1.12303300 0.80990200 1.36856800 F 0.89113400 1.53945600 -0.66903900 C 2.19552400 -0.35891800 -0.34998200 F 2.12627000 -1.63625500 0.05399300 F 2.29706400 -0.33386300 -1.68652600 C 3.51180100 0.21962300 0.21362000 F 3.63611000 -0.04937600 1.50509800 F 4.53857900 -0.32775900 -0.42704900 F 3.55523400 1.53488500 0.03840100 F -1.72969000 1.15929600 -1.15198400 O -2.94009400 -1.47061200 -0.45707500 H -3.83934800 -1.40697600 -0.84557600 O -4.95766300 -0.02967300 -0.79863600 INT28 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1491.588193 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046879 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.110902 a.u. G = E(DMSO) + Gcorr= -1491.541314 a.u. H = E(DMSO) + Hcorr= -1491.477291 a.u. C 3.88036100 -0.31423500 0.58217600 C 2.82325000 0.03112100 -0.53684500 C 1.42146000 -0.13014900 -0.02556300 C 0.43294000 0.74589800 0.05331100 F 3.00408100 1.36660800 -0.87697300 F 0.54173100 1.99342600 -0.40502100 O 3.70075800 0.21608900 1.67993900 C -0.93721200 0.46267100 0.61577500 F -1.46673600 1.61056900 1.07820100 F -0.88158900 -0.41828100 1.62786600 C -1.89159900 -0.10239300 -0.45561600 F -1.93229500 0.76440100 -1.47853100 F -1.39571400 -1.26976600 -0.88839000 C -3.34249000 -0.35936000 -0.00546200 F -3.92266500 0.76506100 0.38586000 F -4.02288100 -0.85271100 -1.03345800 F -3.37691500 -1.23676700 0.98643800 F 1.20997600 -1.37444300 0.40959100 O 3.02004500 -0.75737600 -1.62546800 107 H 3.88055200 -1.18855700 -1.42163200 O 4.77747800 -1.07691800 0.17112100 INT29 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1491.08802 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.032457 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.096837 a.u. G = E(DMSO) + Gcorr= -1491.055563 a.u. H = E(DMSO) + Hcorr= -1490.991183 a.u. C 3.95028000 -0.51309400 0.31135500 C 2.87091000 0.11907300 -0.63611500 C 1.47203700 -0.17315500 -0.06912700 C 0.48130800 0.59247100 0.37229800 F 3.04232200 1.63124500 -0.23526000 F 0.58037600 1.92844700 0.49670500 O 3.51875400 -0.88419500 1.42912400 C -0.89381300 0.12017900 0.75007300 F -1.41662600 0.95419900 1.67730700 F -0.88248100 -1.12029800 1.27384500 C -1.86191900 0.10851600 -0.45043600 F -1.87004500 1.33467900 -0.99838000 F -1.40760900 -0.77074600 -1.35519400 C -3.32581600 -0.26507700 -0.15064100 F -3.87978100 0.60667800 0.67931400 F -4.01002500 -0.25465900 -1.29018300 F -3.40547200 -1.47867100 0.37647200 F 1.18668300 -1.48052600 -0.19865500 O 2.91866300 -0.04177800 -1.88160600 O 5.11333300 -0.58485200 -0.12228900 INT30 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1326.96338 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.022378 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.080251 a.u. G = E(DMSO) + Gcorr = -1326.941002 a.u. H = E(DMSO) + Hcorr = -1326.883129 a.u. C -3.47176500 0.74020000 -0.51052300 C -2.60354900 -0.25360200 -0.31438500 C -1.34945800 -0.34381400 0.48991800 C -0.08346500 0.01459200 -0.32123200 C 1.25065800 -0.39262300 0.34775400 108 F -2.80126700 -1.42900600 -0.99688700 F -1.15679600 -1.60941400 0.95531700 F -1.38210000 0.47618500 1.55954400 F -0.14146100 -0.60195000 -1.51316700 F -0.07602400 1.34202600 -0.53190000 F 1.45289200 -1.70182000 0.15415300 F 1.20335000 -0.15196600 1.66476000 F -3.09910200 1.87979000 0.21170900 C 2.47490500 0.35763100 -0.21929600 F 3.58377000 -0.23441400 0.20247800 F 2.45315800 0.33270200 -1.54592600 F 2.48536200 1.61627800 0.19176200 INT31 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1327.4713 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.035704 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.094259 a.u. G = E(DMSO) + Gcorr = -1327.435596 a.u. H = E(DMSO) + Hcorr = -1327.377041 a.u. C -3.30856900 0.76929600 -0.47225000 C -2.55846500 -0.30643600 -0.33208800 C -1.32015600 -0.43751500 0.51244400 C -0.05651000 -0.01923700 -0.27519600 C 1.27927700 -0.14274100 0.48879400 F -2.85260300 -1.41748400 -1.01471800 F -1.17934700 -1.71790300 0.89734700 F -1.40856000 0.33566800 1.60721200 F 0.00376500 -0.78600500 -1.37504200 F -0.21391700 1.26235500 -0.63862100 F 1.44367600 -1.40620900 0.89846300 F 1.25029400 0.66997500 1.55188900 F -3.01521300 1.89668500 0.16959800 H -4.18737200 0.81050400 -1.10273400 C 2.53117700 0.23125800 -0.33760900 F 3.59544700 0.10352600 0.44395900 F 2.66837900 -0.57681500 -1.37751900 F 2.46217200 1.48306700 -0.76277200 INT32 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1403.431621 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.048638 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.109148 a.u. G = E(DMSO) + Gcorr = -1403.382983 a.u. 109 H = E(DMSO) + Hcorr = -1403.322473 a.u. C 3.23094800 -0.17918300 -0.45600100 C 2.36769500 0.80003500 0.21252300 C 1.08532500 0.33852100 0.76426400 C -0.17469600 0.41359200 -0.15051300 C -1.35320600 -0.47392700 0.32100700 F 2.05683900 1.83180100 -0.73397300 F 0.69048000 1.08448900 1.87364700 F 1.17120600 -0.94237300 1.21531300 F -0.61928600 1.68607300 -0.21488700 F 0.12311000 0.01803000 -1.39738200 F -1.50715200 -0.40616800 1.65096200 F -1.10543400 -1.74710500 -0.01928600 F 2.55796800 -1.06136900 -1.41280400 H 3.93494100 0.35039400 -1.10209100 O 3.85449200 -1.02984300 0.43306900 H 4.42331700 -1.62160400 -0.07584600 C -2.70980500 -0.08687200 -0.30799100 F -3.58857900 -1.05441300 -0.07310600 F -2.59201800 0.07040400 -1.62026900 F -3.17288600 1.03584900 0.22218900 INT33 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1303.465409 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.048309 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10697 a.u. G = E(DMSO) + Gcorr = -1303.4171 a.u. H = E(DMSO) + Hcorr = -1303.358439 a.u. C -3.40871400 -0.65293200 -0.39597500 C -2.53699300 0.34132200 -0.29137500 C -1.27936100 0.38674600 0.51217200 C -0.03129400 0.00458900 -0.31659300 C 1.31392300 0.37320800 0.35221800 F -2.72723200 1.46647400 -1.01184800 F -1.34931900 -0.45193400 1.55847400 F -1.07282600 1.63952200 0.98270100 F -0.06547800 -1.31898300 -0.53751100 F -0.09106200 0.63557900 -1.49913900 F 1.25931200 0.11659100 1.66538500 F 1.54238200 1.67902000 0.17334400 H -4.26866700 -0.51585900 -1.04424100 O -3.27544900 -1.81968500 0.25437800 110 H -4.02904200 -2.38668700 0.04402400 C 2.51652400 -0.40021000 -0.23048400 F 2.48428200 -0.35876100 -1.55640400 F 2.49676900 -1.66299400 0.16613400 F 3.64059200 0.16034100 0.19057800 INT34 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1302.996352 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.034948 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.092916 a.u. G = E(DMSO) + Gcorr = -1302.961404 a.u. H = E(DMSO) + Hcorr = -1302.903436 a.u. C -3.48302800 -0.73685300 -0.35404800 C -2.58296400 0.29816900 -0.22843400 C -1.32557300 0.34561300 0.51433100 C -0.05677500 0.00747700 -0.31178700 C 1.29139800 0.36593000 0.35740600 F -2.72913600 1.39515600 -1.06605100 F -1.33915900 -0.51386400 1.55660700 F -1.07728000 1.60540700 1.01884000 F -0.06276500 -1.31290300 -0.57655400 F -0.10526000 0.66658500 -1.48327700 F 1.25202600 0.09272500 1.66930200 F 1.52657200 1.67528200 0.19719300 H -4.28016000 -0.48121700 -1.08416300 O -3.51576300 -1.84468500 0.22785400 C 2.49632700 -0.39489300 -0.23559600 F 2.46592500 -0.34148800 -1.56175300 F 3.62187700 0.16552400 0.18817100 F 2.48830500 -1.66286300 0.14753300 INT35 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1202.995254 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033674 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.090349 a.u. G = E(DMSO) + Gcorr = -1202.96158 a.u. H = E(DMSO) + Hcorr = -1202.904905 a.u. C -3.71295900 -0.41482400 0.38207300 C -2.30535500 -0.56888300 -0.07131200 C -1.42550000 0.40661800 -0.26240500 C 0.00661000 0.22778200 -0.71423000 111 C 0.94886200 -0.01483100 0.48337200 F -1.94384800 -1.83419500 -0.28379700 F -1.73769300 1.66942800 -0.02882200 F 0.11790300 -0.81062500 -1.55465500 F 0.40535100 1.34295400 -1.34708100 F 0.60694100 -1.17816700 1.05209400 F 0.76838600 0.97797800 1.36587400 H -4.24939400 -1.37257100 0.47379900 O -4.21719700 0.64701400 0.62494500 C 2.45312900 -0.07738100 0.15261900 F 2.69582600 -1.02202800 -0.74323200 F 2.87796000 1.08718000 -0.31250400 F 3.12009000 -0.36079600 1.26389400 INT36 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.950611 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.04664 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.105728 a.u. G = E(DMSO) + Gcorr = -1278.903971 a.u. H = E(DMSO) + Hcorr = -1278.844883 a.u. C -3.48659200 -0.14403000 0.58515000 C -2.05037400 -0.37155300 0.09002000 C -1.11431800 0.50067000 -0.26249800 C 0.28168000 0.16408600 -0.71242200 C 1.26133900 0.04565000 0.47353300 F -1.70526100 -1.67286500 0.04225200 F -1.29964600 1.82637500 -0.20949700 F 0.32720300 -0.99374000 -1.39619900 F 0.74012600 1.14354600 -1.52253300 F 0.89210500 -1.00361700 1.22192200 F 1.16872400 1.16317200 1.21240000 H -3.56529800 -0.82406700 1.46723500 O -3.82564600 1.09449100 0.76500500 O -4.30121300 -0.85080900 -0.42027300 H -4.61435600 -0.11845700 -0.96665800 C 2.74907200 -0.14479300 0.12045200 F 2.92167900 -1.22040400 -0.63476500 F 3.22306200 0.91506500 -0.51762500 F 3.43753000 -0.30276600 1.24584000 INT37 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.999481 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046262 a.u. 112 Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.103647 a.u. G = E(DMSO) + Gcorr = -1278.953219 a.u. H = E(DMSO) + Hcorr = -1278.895834 a.u. C 3.38311700 0.90695200 -0.38062200 C 2.11874800 0.83336200 0.08547800 C 1.43628100 -0.45980800 0.31714800 C 0.00936900 -0.57368500 -0.31216900 C -1.18327600 -0.03874800 0.51943400 F 1.40650600 1.97619900 0.33493400 F 1.13988700 -0.61794200 1.71997200 F 0.00157600 0.06360800 -1.50711100 F -0.27212400 -1.86810400 -0.55658400 F -0.88022300 1.09633100 1.15962500 F -1.53750800 -0.96149200 1.42696400 H 3.80567200 1.90518500 -0.53919600 O 4.11099300 -0.13595900 -0.64946300 O 2.18858900 -1.47879400 -0.10352700 H 3.15837500 -1.05137600 -0.37695200 C -2.43622000 0.25632500 -0.33493400 F -3.47948600 0.43628900 0.46771000 F -2.27044200 1.35736900 -1.05434000 F -2.70027600 -0.75805500 -1.14960800 INT38 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1178.543293 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033347 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.089702 a.u. G = E(DMSO) + Gcorr = -1178.509946 a.u. H = E(DMSO) + Hcorr = -1178.453591 a.u. C -3.66129800 -0.57836500 0.26114100 C -2.30493500 -0.48179700 -0.13625900 C -1.48688900 0.64841900 -0.14286100 C -0.01537500 0.46064100 -0.62982400 C 0.90728600 -0.09181400 0.47122700 F -1.76778500 -1.68361500 -0.55937300 F 0.08888400 -0.34511100 -1.71129000 F 0.48249900 1.66221500 -0.98769100 F 0.53117500 -1.33903700 0.79023600 F 0.78785000 0.68611100 1.56055900 H -4.05257600 -1.61104900 0.15905500 O -4.39266300 0.31528200 0.67977900 113 O -1.78242900 1.79328500 0.20687600 C 2.40942900 -0.15415200 0.13047800 F 2.62037700 -0.89463500 -0.94934100 F 2.90755900 1.05722900 -0.07086500 F 3.05655300 -0.70705400 1.15268700 INT39 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1254.450677 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046842 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.104407 a.u. G = E(DMSO) + Gcorr = -1254.403835 a.u. H = E(DMSO) + Hcorr = -1254.34627 a.u. C -3.60472400 0.20469600 -0.31570100 C -2.26286100 0.11700700 -0.55118000 C -1.13388700 -0.71751300 -0.00605600 C -0.09929200 0.26748100 0.76418600 C 1.20180500 0.70014200 0.05867100 F -1.77125100 1.12676800 -1.41133900 F -0.69434200 1.44366600 1.13009100 F 0.31340300 -0.29004200 1.93284000 F 0.93484400 1.35813800 -1.07630100 F 1.82633700 1.58993400 0.87528100 H -4.03316800 1.03943000 -0.92086000 O -4.40896600 -0.45899100 0.41411900 O -1.44925200 -1.72750000 0.73321000 O -0.29903800 -1.12504500 -1.17772100 H -0.24291000 -2.07464400 -1.01635300 C 2.24590600 -0.42700200 -0.24917300 F 3.44517800 -0.06928500 0.22493600 F 1.93979700 -1.58574400 0.31962900 F 2.38963800 -0.61136400 -1.55337500 INT40 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1254.44469 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.045437 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10404 a.u. G = E(DMSO) + Gcorr = -1254.399253 a.u. H = E(DMSO) + Hcorr = -1254.34065 a.u. C -3.47237900 -0.76819300 0.18740600 C -2.15173700 -0.55488300 -0.47439400 C -1.47766400 0.72081500 0.21940100 114 C 0.06222600 0.69941300 -0.29405000 C 1.12831800 -0.03062400 0.55787600 F -1.43279200 -1.75887200 -0.26905300 F 0.20256300 0.20119000 -1.57655600 F 0.54060600 1.97584300 -0.36784900 F 0.72886100 -1.22041900 1.03209900 F 1.48899600 0.73952400 1.60524900 H -3.41041500 -1.33381400 1.13432700 O -4.53788000 -0.38306500 -0.22984500 O -1.44382700 0.57386600 1.54789600 O -2.06421500 1.77510000 -0.33605900 H -2.24518300 -0.42283300 -1.55058200 C 2.44210500 -0.33513000 -0.19958300 F 2.28489500 -1.32838700 -1.06945800 F 2.89831600 0.73043100 -0.85117200 F 3.38164100 -0.71252600 0.67233900 INT41 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1839.732628 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.039458 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10878 a.u. G = E(DMSO) + Gcorr = -1839.69317 a.u. H = E(DMSO) + Hcorr = -1839.623848 a.u. C -4.02391400 -0.36619900 -0.10673400 C -2.73116200 0.20918900 0.51308300 C -1.48464300 0.00459000 -0.38299400 C -0.16059400 0.12977000 0.41085200 C 1.07731200 0.40503200 -0.47282000 F -4.12355500 0.00379200 -1.37677700 F -4.02755600 -1.68768300 -0.03658000 F -5.06893300 0.09943600 0.56085000 F -2.54126700 -0.38823900 1.69635500 F -2.91452700 1.51859000 0.70730000 F -1.54507100 -1.21697000 -0.93243800 F -1.52214200 0.91663700 -1.36209500 F 0.02387500 -1.01599600 1.07877900 F -0.28227300 1.13132600 1.29787600 F 0.99834600 -0.41559300 -1.54983600 F 0.98036600 1.66406400 -0.95231100 O 2.16705200 0.21067300 0.26021900 C 3.40284000 0.53199500 -0.43922400 F 3.86334700 1.68585900 0.25162000 C 4.32659600 -0.53868600 0.06359000 F 5.58630100 -0.31234400 -0.34985000 115 F 4.41211500 -0.67473800 1.41270200 F 3.96374900 -1.74586600 -0.40073600 INT42 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1739.723881 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.039301 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.107161 a.u. G = E(DMSO) + Gcorr = -1739.68458 a.u. H = E(DMSO) + Hcorr = -1739.61672 a.u. C 3.79938800 0.13085900 -0.25179500 C 2.48718100 -0.49056800 0.27556200 C 1.22154800 0.22190400 -0.26101000 C -0.03010400 -0.08038200 0.60177400 C -1.35431500 0.20231500 -0.13915000 F 3.72098200 0.30493400 -1.56460000 F 4.02891700 1.29636100 0.33020000 F 4.80423400 -0.68775700 0.01654100 F 2.50290500 -0.42537900 1.61264400 F 2.45387300 -1.77059200 -0.10298500 F 1.42911700 1.54450100 -0.26150200 F 1.00820800 -0.18059300 -1.51891900 F 0.01811100 0.68201600 1.69672800 F -0.02137200 -1.37005000 0.96150700 F -1.28992700 1.40095200 -0.72961200 F -1.54745000 -0.70981800 -1.09285200 O -2.36018100 0.15486900 0.79000800 C -3.59704400 0.44953600 0.31277300 F -3.93042400 1.72884600 0.37281400 C -4.43939100 -0.46460800 -0.11861500 F -4.15136700 -1.73783500 -0.18310800 F -5.65271200 -0.19261700 -0.51877800 INT43 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1815.715991 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.051117 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.121299 a.u. G = E(DMSO) + Gcorr = -1815.664874 a.u. H = E(DMSO) + Hcorr = -1815.594692 a.u. C -4.02018400 -0.36665900 -0.10709300 C -2.72612500 0.20164600 0.51673900 C -1.48238600 0.01048900 -0.38612400 C -0.15583000 0.12476700 0.40507800 116 C 1.07867200 0.41538000 -0.47908100 F -4.12242400 0.01836100 -1.37242900 F -4.02324200 -1.68888500 -0.05272500 F -5.06395900 0.09070300 0.56801400 F -2.53152000 -0.41187600 1.69103500 F -2.90983800 1.50802800 0.72968600 F -1.54404600 -1.20297100 -0.95292900 F -1.52258200 0.93660400 -1.35176000 F 0.03346100 -1.03111900 1.05429500 F -0.27480000 1.11171000 1.30866000 F 0.99362500 -0.38371600 -1.57108400 F 0.98214600 1.68371000 -0.93226700 O 2.17268100 0.20528200 0.24178900 C 3.42406600 0.53309500 -0.45652800 F 3.85440400 1.68868200 0.25793600 C 4.33360000 -0.54853800 0.09657500 F 5.61274800 -0.29826300 -0.28892000 F 4.00565500 -1.73451600 -0.51240600 O 4.37213100 -0.74682700 1.44218100 H 3.52398700 -0.46679700 1.81489000 INT44 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1715.718778 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.050346 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.119337 a.u. G = E(DMSO) + Gcorr = -1715.668432 a.u. H = E(DMSO) + Hcorr = -1715.599441 a.u. C -3.76904300 0.40779900 0.17837300 C -2.53593100 -0.42270200 -0.24184500 C -1.19977400 0.18635200 0.24792000 C 0.01797000 -0.36809300 -0.53345600 C 1.35443600 -0.17463000 0.21357200 F -3.68388400 0.72677700 1.46322600 F -3.85049700 1.51511000 -0.54085100 F -4.86234100 -0.31222300 -0.01756400 F -2.52441600 -0.50476200 -1.57798900 F -2.66512600 -1.64775800 0.27334500 F -1.23808400 1.51509800 0.08854400 F -1.05915900 -0.08802200 1.54985900 F 0.08958100 0.26478100 -1.70747000 F -0.15077600 -1.67871900 -0.74823000 F 1.42425900 1.08178600 0.68037300 F 1.41843400 -0.99771800 1.26005900 O 2.36434900 -0.41826000 -0.67645400 117 C 3.61488600 -0.45453600 -0.12513400 F 3.99357500 -1.65328000 0.30897400 C 4.42175200 0.59232700 -0.10502700 F 5.64216900 0.46667800 0.37803800 O 4.19317200 1.83065900 -0.52140800 H 3.31044600 1.91197500 -0.91635600 INT45 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1791.697331 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.062912 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.134013 a.u. G = E(DMSO) + Gcorr = -1791.634419 a.u. H = E(DMSO) + Hcorr = -1791.563318 a.u. C -4.03339000 -0.34353900 -0.09695600 C -2.73181900 0.21887000 0.51640100 C -1.49103500 -0.00272800 -0.38368100 C -0.16203100 0.11073900 0.40368400 C 1.07678300 0.36818300 -0.48430700 F -4.13481800 0.02552400 -1.36717700 F -4.05125400 -1.66487800 -0.02478600 F -5.07051300 0.13428400 0.57445000 F -2.54500600 -0.37704200 1.70091900 F -2.89998600 1.53090100 0.70750800 F -1.56822700 -1.22585100 -0.92806400 F -1.52414800 0.90568100 -1.36646800 F 0.01036200 -1.03429500 1.07653100 F -0.27049400 1.11735300 1.28737700 F 0.97987900 -0.45933500 -1.55894200 F 0.98465700 1.62537200 -0.97492600 O 2.16496300 0.16671000 0.24220300 C 3.40258300 0.47397000 -0.46257200 F 3.82517200 1.68489600 0.18517000 C 4.37883900 -0.55519800 0.06969900 F 4.26734800 -0.72490500 1.46163000 O 5.68127200 -0.18819600 -0.17124100 H 5.75307800 0.75879800 0.01469300 O 4.14325000 -1.79813900 -0.45388600 H 3.66472000 -1.66292000 -1.28390500 INT46 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1691.712462 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.062661 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.1321 a.u. 118 G = E(DMSO) + Gcorr = -1691.649801 a.u. H = E(DMSO) + Hcorr = -1691.580362 a.u. C -3.77387500 0.41451300 0.18292700 C -2.54372200 -0.41710300 -0.24333300 C -1.20493400 0.18445400 0.24871900 C 0.01082200 -0.36656300 -0.53788100 C 1.34928000 -0.18335200 0.20828300 F -3.68783200 0.72474000 1.46992600 F -3.85263700 1.52690300 -0.52884900 F -4.86982500 -0.30068800 -0.01730700 F -2.53559600 -0.49196800 -1.57999600 F -2.67723400 -1.64481200 0.26518200 F -1.24195800 1.51490100 0.10011500 F -1.06626900 -0.09985100 1.54903400 F 0.07791600 0.27431700 -1.70829400 F -0.16602400 -1.67556400 -0.76384500 F 1.41072400 1.06149600 0.70090600 F 1.40310200 -1.02479400 1.24805100 O 2.35267000 -0.42524200 -0.67999000 C 3.60511500 -0.43794800 -0.13508900 F 4.00405100 -1.64938000 0.28861600 C 4.43767100 0.59425400 -0.11525200 O 5.68293400 0.54504000 0.38310000 H 5.83475900 -0.29820000 0.83765800 O 4.10156200 1.77480400 -0.64176700 H 4.60001800 2.47416600 -0.19049300 INT47 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1691.254953 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.05056 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.118592 a.u. G = E(DMSO) + Gcorr = -1691.204393 a.u. H = E(DMSO) + Hcorr = -1691.136361 a.u. C 3.77541300 0.32838700 -0.12975000 C 2.48548000 -0.28098300 0.46284000 C 1.21633200 0.06619600 -0.35374800 C -0.08378900 -0.13076000 0.46494400 C -1.35515900 -0.27013500 -0.40146000 F 3.82136300 0.11560800 -1.43842900 F 3.82582600 1.63025000 0.10168400 F 4.82534100 -0.24669600 0.43745400 119 F 2.35594800 0.17114300 1.71667200 F 2.63270900 -1.60914000 0.48869000 F 1.29123000 1.34629100 -0.74519600 F 1.19726300 -0.71338200 -1.44199200 F -0.21746500 0.92478500 1.27751500 F 0.04314100 -1.23857000 1.21477200 F -1.29577600 0.67538100 -1.37053300 F -1.30081700 -1.46062800 -1.03869200 O -2.41645700 -0.15135700 0.39023100 C -3.66620200 -0.37961800 -0.27164800 F -4.06371100 -1.66518900 0.11409800 C -4.65345000 0.58853600 0.10603300 O -5.85655900 0.38684000 0.19869000 O -4.15486900 1.84893800 0.22986300 H -4.92413400 2.42621600 0.34206500 INT48 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1364.208256 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.022959 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.079972 a.u. G = E(DMSO) + Gcorr = -1364.185297 a.u. H = E(DMSO) + Hcorr = -1364.128284 a.u. C -2.53042600 -0.26463400 0.07187500 C -1.22385100 0.50964300 -0.21082600 C 0.05411100 -0.33545900 0.02199600 C 1.32433900 0.52800800 0.20000700 C 2.70507500 -0.16409500 -0.00665800 F -2.49172600 -1.46278700 -0.49699200 F -2.71762900 -0.40929800 1.37474300 F -3.55464100 0.41303900 -0.42916900 F -1.21847700 1.58923000 0.58386600 F -1.25837900 0.90946800 -1.48779200 F -0.13799700 -1.07603400 1.12834300 F 0.17740600 -1.16283800 -1.02446100 F 1.27509600 1.02699000 1.45247100 F 1.23059000 1.57411700 -0.65551700 F 2.49021600 -1.48193100 0.55556100 F 2.70524700 -0.48916700 -1.40679500 O 3.69089400 0.43526300 0.39916200 INT49 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1264.18692 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.021739 a.u. 120 Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.077517 a.u. G = E(DMSO) + Gcorr = -1264.165181 a.u. H = E(DMSO) + Hcorr = -1264.109403 a.u. C -2.34178700 -0.30707500 -0.02465800 C -1.05494400 0.54737400 -0.02744700 C 0.23212200 -0.30353700 -0.15679300 C 1.49775600 0.44655400 0.31826800 C 2.77848200 -0.22473800 -0.20947400 F -2.29281400 -1.19616900 -1.00848100 F -2.47825800 -0.94021800 1.12878100 F -3.38747300 0.48298800 -0.20700700 F -1.01546600 1.25035800 1.11054700 F -1.11831300 1.38997400 -1.06110500 F 0.10292400 -1.42542600 0.56081500 F 0.40157900 -0.62833800 -1.44582100 F 1.52251100 0.46538600 1.65576000 F 1.45306500 1.69674800 -0.14756500 F 2.96632800 -1.38730600 0.39580100 O 3.49293700 0.20956900 -1.02936200 INT50 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1791.697331 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.062912 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.134013 a.u. G = E(DMSO) + Gcorr = -1791.634419 a.u. H = E(DMSO) + Hcorr = -1791.563318 a.u. C -2.54150700 -0.26658600 0.05831300 C -1.22853100 0.51108700 -0.18224300 C 0.04535600 -0.34922700 0.01484400 C 1.32226100 0.49940100 0.22466300 C 2.70656200 -0.18512400 -0.00816800 F -2.51535700 -1.43283500 -0.57410900 F -2.73333100 -0.47923100 1.35145000 F -3.56006900 0.44639500 -0.40594300 F -1.22434600 1.55176200 0.66365200 F -1.25958400 0.97179400 -1.43935500 F -0.15698900 -1.12966700 1.09272800 F 0.15394100 -1.13992000 -1.06140900 F 1.27093300 0.93673100 1.50511100 F 1.21587600 1.59344400 -0.56831600 F 2.65284300 -0.38315800 -1.49049700 O 3.69283100 0.48826700 0.35047000 121 O 2.57604200 -1.48878500 0.49742000 H 3.42891200 -1.67099000 0.91262400 INT51 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1502.648099 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.039227 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10129 a.u. G = E(DMSO) + Gcorr = -1502.608872 a.u. H = E(DMSO) + Hcorr = -1502.546809 a.u. C 3.92154100 -0.07225400 -0.44997100 C 2.69189400 -0.16657100 0.47967800 C 1.34517400 -0.01817200 -0.27069400 C 0.17883500 0.35861300 0.67779400 C -1.22400500 0.05699600 0.09878000 F 3.75032200 -0.84431400 -1.51508400 F 4.11439400 1.17642600 -0.84325300 F 4.99418200 -0.48155500 0.21117800 F 2.80468400 0.79566000 1.40448400 F 2.72222300 -1.35934900 1.08181700 F 1.47165300 0.94139200 -1.19917100 F 1.08541800 -1.17686100 -0.88850600 F 0.27392100 1.66917900 0.93402600 F 0.32153300 -0.31772000 1.82990100 F -1.23188400 0.47755700 -1.18551400 F -1.36539800 -1.29053100 0.05899400 O -2.12623700 0.64603700 0.88785700 C -3.51351400 0.87554900 0.52566800 F -3.47210400 1.76617800 -0.57925400 C -4.11926300 -0.36723000 -0.06245900 F -4.04466000 -1.39835200 0.79326400 F -5.42719500 -0.14906200 -0.31089400 F -3.62754400 -0.82752600 -1.24705700 INT52 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1853.044898 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047232 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.11804 a.u. G = E(DMSO) + Gcorr =corr = -1852.997666 a.u. H = E(DMSO) + Hcorr = -1852.926858 a.u. C -2.94947900 -0.83186100 -0.50895000 C -1.79047700 0.00799900 -0.23720500 C -0.82230800 -0.10847600 0.72505300 122 C 0.35932300 0.89796200 0.64962200 C 1.46716500 0.52158800 -0.35002800 F -1.66427500 1.02111400 -1.17423700 F 0.00777000 2.17295100 0.33295800 F 0.96670700 0.97848000 1.85752200 F 2.50533300 1.37105300 -0.19589800 F 1.01442200 0.65100400 -1.60738600 H -3.30167100 -0.71166200 -1.54613900 O -3.26409700 -1.82909600 0.14974900 O -0.70171500 -0.95439100 1.65018100 C 2.03829900 -0.90181600 -0.22358300 F 2.46299600 -1.14456400 1.00779900 F 1.13978600 -1.81069200 -0.56732700 F 3.07759100 -1.01571500 -1.05205100 O -4.44585200 0.66875800 -0.14247100 H -4.81311800 0.10443800 0.54460400 INT53 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1526.687926 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.027651 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.088876 a.u. G = E(DMSO) + Gcorr = -1526.660275 a.u. H = E(DMSO) + Hcorr = -1526.59905 a.u. C 3.56550300 0.08156600 -0.06897200 C 2.17429400 0.54491800 0.34152400 C 0.94646600 -0.33857400 0.00044300 C -0.40734500 0.41502100 0.05472000 C -1.62280900 -0.53525000 0.18643200 F 3.53535500 -1.30917900 0.22082900 F 3.52585900 0.09111800 -1.48204400 F 2.15199400 0.69005200 1.69311000 F 1.94276600 1.76744200 -0.20477200 F 0.87842900 -1.36174400 0.87403900 F 1.06922300 -0.84837800 -1.23548900 F -0.42293000 1.24713200 1.10579600 F -0.55250900 1.13766200 -1.06700400 F -1.72959300 -0.93413300 1.45838600 F -1.44995100 -1.60860100 -0.59626700 C -2.96155500 0.12419500 -0.21193500 F -3.96057000 -0.64743200 0.19208200 F -3.07633700 1.31352400 0.36507800 F -3.04143800 0.26795200 -1.52521800 123 TS1 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1953.064359 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.043547 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.117816 a.u. G = E(DMSO) + Gcorr= -1953.020812 a.u. H = E(DMSO) + Hcorr= -1952.946543 a.u. C 5.26639900 -1.02744200 -0.44095600 O 5.24462100 -1.69568800 0.51083500 O 5.47305900 -0.55548200 -1.48326400 C 3.49279300 0.71512700 0.22183100 C 2.21531900 -0.11407300 0.23781200 C 0.86447100 0.57927700 -0.07360200 C -0.37831900 -0.21760500 0.39840000 C -1.68647200 0.22667800 -0.30408500 C -2.95322900 -0.20579400 0.47556500 F 3.35660700 1.58800400 1.32213500 F 3.31170500 1.58012400 -0.87998900 F 2.08789900 -0.70222100 1.45469700 F 2.33866300 -1.10585800 -0.68603500 F 0.81918400 1.78220100 0.52123700 F 0.75319000 0.75985000 -1.40370200 F -0.53213200 -0.04607800 1.72069800 F -0.19852500 -1.52194000 0.14852100 F -1.70290100 1.56112000 -0.41781800 F -1.72831000 -0.31176400 -1.53029000 F -3.14819700 0.64246100 1.48955400 F -2.78593400 -1.44186100 0.96239200 C -4.23005200 -0.20709100 -0.39301100 F -5.28830000 -0.31602000 0.39604200 F -4.31495300 0.92642900 -1.07727600 F -4.22209700 -1.22612600 -1.23708800 TS2 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1764.447022 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.035404 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.102308 a.u. G = E(DMSO) + Gcorr= -1764.411618 a.u. H = E(DMSO) + Hcorr= -1764.344714 a.u. C -0.82274300 -0.11163400 -0.09904300 C 0.20325900 0.97896100 0.28582200 C -2.27461700 0.43749000 -0.14228400 124 C 1.69236100 0.74541200 -0.11555000 F 0.10397200 1.22314900 1.59278700 F -0.16788100 2.10641300 -0.36532800 F -0.53776700 -0.58812700 -1.31830600 F -0.78239700 -1.10891800 0.79064400 C -3.33731400 -0.68073500 -0.04264500 F -2.46707000 1.08065600 -1.29783900 F -2.47917500 1.28649000 0.87256100 C 2.36530000 -0.57268300 0.22257600 F 1.74282900 0.91116900 -1.45961000 F 2.35679200 1.77581600 0.44318900 F -4.51684600 -0.19033300 -0.39407000 F -3.02580300 -1.67998200 -0.85816000 F -3.42051600 -1.13914500 1.19597300 C 3.72300800 -0.64996500 0.05187500 F 1.63311100 -1.64256100 -0.19744300 F 1.86944200 -0.67662000 1.79144300 F 4.25417600 -1.83329100 -0.36778200 F 4.40429500 0.37738400 -0.53522500 TS3 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1740.477606 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047194 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.115023 a.u. G = E(DMSO) + Gcorr= -1740.430412 a.u. H = E(DMSO) + Hcorr= -1740.362583 a.u. C 2.95074000 1.04895900 0.04882200 C 2.40012100 -0.08645300 -0.49282000 C 1.68908300 -1.16609300 0.18537100 C 0.17858400 -1.32834400 -0.13748800 F 2.15632900 -0.07631700 -1.84936300 F 0.03468300 -1.71038700 -1.41554300 F -0.33170700 -2.30059800 0.64817800 F 1.84046500 2.35805900 0.36846600 C -0.66310000 -0.05466200 0.08586500 F -0.43511700 0.80034700 -0.92069400 F -0.30968800 0.52018600 1.24150900 C -2.18500300 -0.34239600 0.15370500 F -2.52449100 -1.26042500 -0.76085600 F -2.48651500 -0.80931100 1.37007000 C -3.04822400 0.91411800 -0.09645000 F -3.03801500 1.24126200 -1.37889600 F -4.29741500 0.66144600 0.26732400 F -2.58990200 1.93395300 0.61766200 125 F 1.79836700 -1.08890100 1.52698300 F 3.35215100 0.95382800 1.33264500 O 3.77924500 1.76012300 -0.73070800 H 3.57955800 2.69379000 -0.56408500 F 2.19233100 -2.41042700 -0.16662800 TS4 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1640.040513 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033828 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.099765 a.u. G = E(DMSO) + Gcorr = -1640.006685 a.u. H = E(DMSO) + Hcorr = -1639.940748 a.u. C 3.64600700 -0.98767500 -0.32728100 C 2.43813000 -0.46540400 0.27784500 C 1.74322400 0.57128200 -0.21546300 C 0.36278000 0.95668300 0.28505400 F 2.06730800 -1.00740800 1.45156200 F 0.31331600 1.01500100 1.61903500 F -0.01761800 2.13333800 -0.23435600 F 4.13970200 -2.00954700 0.40452000 C -0.68408900 -0.08625100 -0.18618200 F -0.51700400 -1.21656500 0.51590300 F -0.46603800 -0.35292300 -1.48351800 C -2.15070700 0.38731200 -0.03979900 F -2.31006200 1.04701400 1.11412400 F -2.44564400 1.20711200 -1.05411800 C -3.16577300 -0.77781000 -0.06478500 F -3.12910200 -1.45550200 1.07137000 F -4.38542500 -0.28732100 -0.22847300 F -2.89206400 -1.59846600 -1.07107100 F 1.99936000 1.02716100 -1.42132800 O 4.19361500 -0.64306600 -1.31978800 F 2.45589800 2.33763100 0.66990100 TS5 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.504072 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.041853 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10965 a.u. G = E(DMSO) + Gcorr = -1591.462219 a.u. H = E(DMSO) + Hcorr = -1591.394422 a.u. C -3.55065200 -1.10358500 0.30517800 C -2.48993100 -0.38360700 -0.22727100 126 C -1.77385500 0.63902700 0.45404900 C -0.38817600 1.01800200 -0.13633400 F -2.16891200 -0.62442700 -1.54439400 F -0.31388900 1.17719500 -1.46901600 F 0.08197200 2.14154100 0.44759000 O -4.08911600 -1.12153900 1.38551100 O -1.97033700 0.99501200 1.61300700 O -2.52225300 2.52336000 -0.77685800 H -2.96972700 2.70695200 0.05448800 F -4.05851600 -2.00612900 -0.65370200 C 0.64681000 -0.08927500 0.20360200 F 0.46704700 -1.13365900 -0.62919100 F 0.47111000 -0.53151000 1.46036700 C 2.12270700 0.36782600 0.09398500 F 2.29796400 1.16771800 -0.96662800 F 2.45577900 1.04277500 1.20273000 C 3.11929400 -0.80271800 -0.04785500 F 3.05178300 -1.33692700 -1.25823800 F 4.35268300 -0.35107300 0.14357300 F 2.86366800 -1.74057500 0.85581000 TS6 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1592.015604 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.055916 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.123535 a.u. G = E(DMSO) + Gcorr = -1591.959688 a.u. H = E(DMSO) + Hcorr = -1591.892069 a.u. C 3.40535100 1.23498700 -0.23538400 C 3.40730700 -0.05592400 -0.72468400 C 1.50356000 -1.24088100 0.24159400 C 0.51788900 -0.11697800 -0.11523600 F 0.63707000 0.30533400 -1.38221800 O 2.94376000 2.26581800 -0.68160000 O 1.86683700 -1.42423000 1.37334200 O 1.51394400 -2.17159800 -0.72726600 H 2.02788600 -2.92717500 -0.39756300 F 3.97520400 1.30734800 1.04542900 F 0.70580000 0.91668600 0.71883100 F 4.22524400 -0.98939600 -0.11283100 H 3.24336500 -0.25501900 -1.77184000 C -0.94784800 -0.59266700 0.06105800 C -1.95711300 0.57327500 0.19856400 C -3.41449900 0.15476200 -0.09286100 F -1.29513800 -1.34155000 -0.99785800 127 F -1.04515000 -1.35072300 1.16342100 F -1.63937000 1.55900800 -0.65053100 F -1.91169600 1.04324500 1.45001200 F -3.59597000 -0.04130400 -1.38956900 F -3.70808400 -0.96106000 0.56284100 F -4.23185100 1.11717300 0.30972600 TS7 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1840.883225 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.061362 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.130947 a.u. G = E(DMSO) + Gcorr = -1840.821863 a.u. H = E(DMSO) + Hcorr = -1840.752278 a.u. C 1.28199700 0.48196900 0.01129600 C 2.58136500 -0.32209600 0.31363700 C 3.92466500 0.38297900 0.07219300 F 1.37138600 1.08705300 -1.18172000 F 1.03810300 1.38793000 0.97003800 F 3.37062800 1.91229700 0.13843500 F 2.44304900 -1.41330100 -0.47543700 F 2.50322500 -0.68946200 1.60445100 H 4.62225200 0.56517200 0.86682400 O 4.84357300 -1.33028200 0.33403700 H 4.68477200 -1.93440600 -0.39793200 F 4.29097300 0.43970500 -1.21383900 C 0.02369200 -0.43697200 -0.06251000 C -1.29589700 0.35697000 0.12927300 C -2.52948800 -0.41018900 -0.41034900 C -3.86593700 0.10977300 0.16414000 F -3.90870900 1.43348400 0.08591500 F -4.00904900 -0.25787900 1.42701700 F -2.57711600 -0.27632900 -1.73915200 F -2.42687000 -1.70887200 -0.10140500 F -1.21823900 1.52480700 -0.52191500 F -1.47797400 0.59831700 1.43440400 F -0.02872300 -1.03289600 -1.26365000 F 0.07464800 -1.38167200 0.88545800 F -4.86510900 -0.39686000 -0.54273900 TS8 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1740.404938 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.045724 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.114398 a.u. 128 G = E(DMSO) + Gcorr = -1740.359214 a.u. H = E(DMSO) + Hcorr = -1740.29054 a.u. C 3.49146300 0.57346600 0.02872900 C 2.67941700 -0.44709100 -0.24436400 C 1.25319800 -0.45129200 0.24428400 C 0.39226200 0.66576700 -0.39373900 F 2.85291500 -1.07150100 -1.42627100 F 0.93431000 1.86369500 -0.11975300 F 0.38861400 0.49526800 -1.72558700 F 4.72536500 0.66661400 -0.47134800 C -1.08179600 0.78630800 0.08049800 F -1.63455600 1.75944000 -0.66771500 F -1.08722200 1.18572100 1.35820900 C -1.98020400 -0.46608800 -0.03437700 F -1.75526100 -1.09942500 -1.19092900 F -1.71326000 -1.28585200 0.98765100 C -3.48995200 -0.12948600 0.02256100 F -3.89108000 0.42406500 -1.11058000 F -4.16995900 -1.25121600 0.21103800 F -3.74210400 0.69994800 1.02622000 F 1.17270100 -0.28721700 1.57521100 F 3.34209600 1.37941600 1.08198900 F 0.64857200 -1.60304400 -0.10419200 O 3.12033800 -2.14494300 0.82837000 H 2.81079600 -2.91318000 0.33600500 TS9 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.501492 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.04165 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.109539 a.u. G = E(DMSO) + Gcorr = -1591.459842 a.u. H = E(DMSO) + Hcorr = -1591.391953 a.u. C 3.70177600 -0.49399300 -0.55162500 C 2.39737500 -0.22024900 -0.00750200 C 1.60707800 0.85679900 -0.33651100 C 0.22807100 0.93509200 0.38576300 F 1.96079600 -1.11274800 0.93918500 F 0.28613200 0.65151100 1.70927400 F -0.25460900 2.19624000 0.28705200 O 4.31137700 0.11591000 -1.38224200 O 1.81649800 1.77142500 -1.15994700 O 4.80120100 0.00853400 1.41509400 129 H 4.95931700 0.90302900 1.09772300 F 4.04061300 -1.82603000 -0.34987800 C -0.84250000 0.01998100 -0.24436600 F -0.63109400 -1.25215200 0.13285000 F -0.74385200 0.08295500 -1.58316400 C -2.29749300 0.39948100 0.12594600 F -2.37495600 0.73792500 1.42035700 F -2.68405200 1.44289100 -0.61888600 C -3.31059900 -0.74052200 -0.11491800 F -3.18101300 -1.68954600 0.79956700 F -4.54161800 -0.25088700 -0.04225800 F -3.13125600 -1.27010700 -1.31873200 TS10 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.488496 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.043511 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.11051 a.u. G = E(DMSO) + Gcorr= -1591.444985 a.u. H = E(DMSO) + Hcorr= -1591.377986 a.u. C -3.71864800 -1.15747200 0.25941900 C -2.46871100 -0.50653000 -0.26961400 C -1.80838600 0.57653400 0.17981500 C -0.41834100 0.93219300 -0.30653100 F -2.03089000 -0.98910600 -1.48034100 F -0.31819300 1.00167100 -1.64184600 F -0.00149200 2.10760000 0.22107800 O -4.20161500 -2.05446000 -0.46682400 C 0.63823500 -0.10050000 0.17087600 F 0.51296500 -1.23767700 -0.53258800 F 0.42672100 -0.38239000 1.46848600 C 2.10379700 0.38759000 0.04487300 F 2.27993600 1.06045700 -1.10042200 F 2.38985200 1.19933300 1.07082100 C 3.13312100 -0.76411200 0.06884400 F 3.11540300 -1.43858300 -1.07048300 F 4.34782300 -0.25871900 0.23975200 F 2.87044700 -1.59441800 1.07043600 F -1.98164900 0.99929700 1.44155200 O -2.53581400 2.36858000 -0.64389300 H -2.23149100 3.09603400 -0.09010500 O -4.14172300 -0.75280100 1.36396700 TS11 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1567.522204 a.u. 130 Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.059366 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.124625 a.u. G = E(DMSO) + Gcorr= -1567.462838 a.u. H = E(DMSO) + Hcorr= -1567.397579 a.u. C 4.22569300 0.32017900 -0.22307700 C 2.90580200 -0.44245700 -0.34021500 C 1.67955800 0.31765300 -0.08100400 C 0.38758800 -0.48845800 0.08236800 F 0.36367100 -1.17490000 1.24826700 O 5.17483100 -0.10445400 -0.89485300 O 1.90833200 0.73853600 -1.34635500 O 1.68865500 1.25978700 0.93843100 H 2.65994100 1.49712800 0.97975300 F 0.28122500 -1.40425800 -0.91264700 F 3.32917800 -1.59581000 1.07887700 H 2.84500800 -1.29116400 -0.99821000 C -0.90094100 0.36892200 0.05862400 C -2.16879900 -0.44413600 -0.30333200 C -3.48632000 0.25730900 0.09199200 F -1.10256300 0.91414300 1.27199100 F -0.79623000 1.36100600 -0.83600200 F -2.15158000 -1.63333900 0.31629900 F -2.20398400 -0.64284400 -1.62726100 F -3.66505300 0.22533000 1.40392500 F -3.47949100 1.52018900 -0.31556200 F -4.50242200 -0.37154200 -0.48547900 O 4.22628100 1.31590600 0.55585800 TS12 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1467.546213 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.058277 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.121759 a.u. G = E(DMSO) + Gcorr= -1467.487936 a.u. H = E(DMSO) + Hcorr= -1467.424454 a.u. C 4.03422600 0.67851000 0.29366600 C 2.88094900 -0.27492900 0.57177900 C 1.84012600 -0.19532900 -0.48619500 C 0.50093600 -0.86060800 -0.13570600 F 0.44689300 -1.33115300 1.12824200 O 5.13709500 0.36494500 -0.05062600 O 3.03266900 -1.58118300 0.22710800 O 1.96514800 0.23512600 -1.62027700 131 H 2.80627100 2.07789300 0.73591000 F 0.22386300 -1.87849300 -0.97642400 H 2.53219000 -0.06946200 1.60004300 C -0.64727000 0.16789200 -0.26470900 C -1.95276200 -0.26712400 0.44464100 C -3.20085300 0.49825400 -0.04611500 F -0.25078800 1.32866400 0.29005800 F -0.92217300 0.38661100 -1.55887500 F -1.83673000 -0.04459900 1.75921700 F -2.17177700 -1.57326200 0.24079800 F -2.95472900 1.80218100 -0.07350900 F -3.55640700 0.09745400 -1.25667000 F -4.20671000 0.26903500 0.78686500 O 3.73839400 1.98156300 0.48661500 TS13 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1467.56727 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.056975 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.121283 a.u. G = E(DMSO) + Gcorr= -1467.510295 a.u. H = E(DMSO) + Hcorr= -1467.445987 a.u. C 2.52598700 1.67582300 0.05899500 C 3.12114900 -0.37397700 0.47441900 C 2.04689400 -0.88614100 -0.23441700 C 0.69269800 -0.96990500 0.45158700 F 0.69959800 -0.44745100 1.69924300 O 3.00646300 1.86922200 -1.00447500 O 4.35334000 -0.49059700 -0.11907100 O 2.10209300 -1.27810900 -1.42520300 F 0.32736300 -2.27406500 0.57680600 H 3.13968200 -0.25382000 1.54633500 C -0.43784000 -0.27701200 -0.34831600 C -1.68481400 0.04886600 0.50795100 C -2.95125000 0.32760000 -0.33140900 F 0.01131800 0.87722600 -0.86432600 F -0.82660000 -1.07043700 -1.36030400 F -1.44287800 1.13764600 1.24644500 F -1.96190100 -0.98038800 1.32234000 F -2.67474500 1.17480100 -1.31474300 F -3.43203400 -0.79357900 -0.84673300 F -3.88064200 0.86586900 0.44722700 O 1.96818800 2.06240400 1.03234300 H 4.16740300 -0.72764600 -1.04155900 132 TS14 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.445993 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.032731 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.090135 a.u. G = E(DMSO) + Gcorr= -1278.413262 a.u. H = E(DMSO) + Hcorr= -1278.355858 a.u. C 3.71878500 -0.08205700 -0.51281900 C 2.57336400 0.60433100 -0.03788500 C 1.39548700 -0.14900800 0.22252500 F 1.35403600 -1.41953700 -0.23782400 F 1.11082700 -0.44193300 1.80348200 C 0.02453800 0.47915300 -0.05722200 F -0.11075800 0.58381600 -1.41329800 F -0.11700900 1.71216600 0.44698000 C -1.22904000 -0.30479300 0.44477500 F -1.06340200 -1.63428400 0.44207000 F -1.53204000 0.08001800 1.69450500 C -2.48963500 -0.02777200 -0.40605200 F -2.42149800 -0.63602300 -1.58246600 F -3.55887900 -0.49349200 0.23489900 F -2.65419200 1.27585400 -0.60002100 O 2.58236800 1.92136100 0.18431200 H 4.52233000 0.66020700 -0.73355600 O 3.97424700 -1.29868800 -0.71947500 TS15 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1178.498823 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.030046 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.0876 a.u. G = E(DMSO) + Gcorr= -1178.468777 a.u. H = E(DMSO) + Hcorr= -1178.411223 a.u. C -3.94585700 -0.07634500 -0.26423500 C -2.58783700 0.63111900 -0.31667500 C -1.37580800 -0.15049200 -0.15712700 F -1.50369800 -1.49451100 -0.09745100 C -0.13500400 0.34221400 -0.02020300 F 0.24435800 0.64739600 2.03172400 F 0.11945100 1.61504300 -0.24334900 C 1.07302600 -0.57274300 -0.09889600 F 1.09602500 -1.50733200 0.85441900 F 1.02088400 -1.23828700 -1.28700900 C 2.44330000 0.14220900 -0.12647900 133 F 3.38862700 -0.79351100 -0.21469100 F 2.52405200 0.91306600 -1.20884500 F 2.68726500 0.87713300 0.93857400 O -2.61392500 1.83623200 -0.45712100 H -4.72306600 0.43765500 -0.85517300 O -4.17364100 -1.02428100 0.43168500 TS16 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1153.949929 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.028563 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.085895 a.u. G = E(DMSO) + Gcorr= -1153.921366 a.u. H = E(DMSO) + Hcorr= -1153.869987 a.u. C -3.66984200 0.41110800 -0.07539200 C -2.65505100 -0.73185400 -0.15294500 C -1.01222400 0.32267500 0.00742600 F -0.79581500 1.08969000 -1.11368800 C 0.10262100 0.13949200 0.71679700 F 0.07331900 -0.62380700 1.85300500 C 1.50282700 0.56857700 0.42739700 F 1.56033400 1.75987300 -0.21061200 F 2.22560200 0.69186000 1.57201800 C 2.28685700 -0.41674600 -0.45168900 F 1.71418700 -0.53142300 -1.64538800 F 3.54300600 -0.00813000 -0.63171700 F 2.31977100 -1.61788500 0.12117300 O -2.75490800 -1.48928500 0.88369200 H -4.69187000 0.04478600 -0.33162800 O -3.52417900 1.57457600 0.22808600 O -2.52127500 -1.16602900 -1.36191000 TS17 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.9986 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.058518 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.12484 a.u. G = E(DMSO) + Gcorr= -1591.940082 a.u. H = E(DMSO) + Hcorr= -1591.87376 a.u. C -4.15546600 -0.13610900 -0.38700500 C -2.82725300 0.49947000 -0.27002000 C -1.63881000 -0.31453200 -0.01755300 C -0.34544500 0.49493900 0.15124500 F -0.33687800 1.13878900 1.33604600 O -5.08051500 0.23364800 -1.01706100 134 O -1.93895100 -0.64097900 -1.29695700 O -1.56999400 -1.30901700 0.94162700 H -2.36137600 -1.85751100 0.86913800 F -4.25627300 -1.27861400 0.33667100 F -0.26848100 1.43005600 -0.81944800 F -3.49297300 1.32660600 1.24805500 H -2.70492800 1.43508400 -0.78954500 C 0.94052000 -0.36377700 0.08074200 C 2.19487000 0.45964200 -0.30160000 C 3.52313300 -0.25016100 0.04191000 F 1.16930400 -0.93130600 1.27579100 F 0.79261900 -1.33245400 -0.83284400 F 2.18434000 1.63216300 0.34818600 F 2.18797100 0.68832500 -1.61967200 F 3.74286700 -0.23173300 1.34728700 F 3.49385400 -1.50876700 -0.37761100 F 4.52061500 0.37986800 -0.56321300 TS18 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1567.471645 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.056442 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.12331 a.u. G = E(DMSO) + Gcorr= -1567.415203 a.u. H = E(DMSO) + Hcorr= -1567.348335 a.u. C -3.86474600 -1.04640000 -0.09984100 C -3.61878500 0.10148600 -0.93497800 C -1.51987200 0.91241500 0.43175000 C -0.45982900 -0.07746700 -0.07828200 F -0.56361100 -0.34721600 -1.39058500 O -3.32280900 -2.14411400 -0.47468700 O -1.92788900 0.85627700 1.55963200 O -1.55238200 1.99749600 -0.36133200 H -2.40683400 2.43323700 -0.19146700 F -0.53482400 -1.22240300 0.61475100 F -4.08418900 1.37738800 -0.48216900 H -2.80794400 0.21677900 -1.63421700 C 0.96653500 0.49356100 0.14262200 C 2.07257600 -0.58981300 0.12417200 C 3.48282400 -0.01683500 -0.13633400 F 1.23582200 1.39747000 -0.81355300 F 1.02198000 1.11112300 1.33334800 F 1.81936400 -1.49213600 -0.83284400 F 2.09859800 -1.20800800 1.31035700 F 3.62034900 0.33352000 -1.40569100 135 F 3.69570400 1.04328600 0.63344900 F 4.38889800 -0.94175500 0.14814600 O -4.62445000 -0.93129900 0.91315600 TS19 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.486114 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.043743 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.110753 a.u. G = E(DMSO) + Gcorr= -1591.442371 a.u. H = E(DMSO) + Hcorr= -1591.375361 a.u. C 3.83242000 -0.88441800 -0.39115700 C 2.61306900 -0.23798000 0.27359900 C 1.63649900 0.40306200 -0.38716100 C 0.32321900 0.83935600 0.14865900 F 2.27698200 -0.73066400 1.47312000 F 0.32366600 0.95088200 1.49077800 F -0.02558000 2.05509600 -0.36483700 O 4.11209000 -2.01162300 0.05723700 C -0.83174600 -0.12212600 -0.22372500 F -0.70200900 -1.24000500 0.51220300 F -0.72138200 -0.45641000 -1.52008000 C -2.25311500 0.45157600 -0.01427000 F -2.30799400 1.16543500 1.11814700 F -2.55452000 1.25162600 -1.04498300 C -3.34645700 -0.63528600 0.06684400 F -3.28196600 -1.28315800 1.21972700 F -4.53907200 -0.06363700 -0.03054600 F -3.20383400 -1.50181300 -0.92837700 F 1.77905100 0.78294300 -1.68350700 O 4.06272700 1.19444400 1.33250700 H 4.53097900 1.33053800 0.50362400 O 4.35463500 -0.25635800 -1.32914100 TS20 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.539641 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046228 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.111416 a.u. G = E(DMSO) + Gcorr= -1591.493413 a.u. H = E(DMSO) + Hcorr= -1591.428225 a.u. C 4.12862000 -0.67177500 0.07167400 C 2.92697400 0.33786600 0.22099400 C 1.60156400 -0.28342800 -0.07055200 136 C 0.40095800 0.40888100 0.05321700 F 2.94127100 0.72900000 1.58440500 F 0.32827800 1.16720000 1.17052200 F 0.04981100 1.54012500 -1.04542500 O 4.04817600 -1.75148400 0.66527900 C -0.90614000 -0.38299500 -0.08364100 F -1.06050300 -1.13580500 1.03709400 F -0.86288700 -1.22734500 -1.12820200 C -2.21714800 0.43702500 -0.23885800 F -2.18987200 1.56895200 0.47674400 F -2.42197500 0.73745200 -1.52790600 C -3.46849300 -0.34456300 0.22740100 F -3.53112900 -0.41140200 1.54953600 F -4.55754900 0.28217000 -0.20645100 F -3.46559600 -1.57602500 -0.27018800 F 1.70100100 -1.03489000 -1.25104900 O 3.21211800 1.46148400 -0.52152000 H 4.13989800 1.29683800 -0.79720200 O 5.07526200 -0.21722200 -0.61700200 TS21 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1591.539641 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046228 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.111416 a.u. G = E(DMSO) + Gcorr= -1591.493413 a.u. H = E(DMSO) + Hcorr= -1591.428225 a.u. C 4.07605900 0.59013100 0.36860000 C 3.64548700 -0.74330400 -0.31489600 C 1.37119400 -0.33971500 0.05851400 C 0.37087400 0.52730300 -0.09467200 F 3.56674300 -0.61815300 -1.69831300 F 0.54121600 1.58402800 -0.95427800 O 4.09141300 0.54546500 1.60861300 C -1.01373900 0.54244400 0.46510700 F -1.47554700 1.81519500 0.58254900 F -1.06453300 -0.01863200 1.69266000 C -2.02277700 -0.21832900 -0.41923300 F -1.95696800 0.27494700 -1.66795300 F -1.67260200 -1.51390500 -0.44598300 C -3.50101300 -0.16020400 0.00778500 F -3.96782900 1.07881600 -0.05586200 F -4.21805000 -0.91958900 -0.81626900 F -3.65630700 -0.61895500 1.24221700 F 1.03374300 -1.38360500 0.89722500 137 O 3.79662000 -1.84797100 0.11384600 O 4.39630200 1.51359800 -0.39885600 TS22 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1403.378123 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.042692 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.105958 a.u. G = E(DMSO) + Gcorr = -1403.335431 a.u. H = E(DMSO) + Hcorr = -1403.272165 a.u. C 3.13720700 -0.50396000 -0.67834000 C 2.17523700 0.39481000 -0.49616700 C 0.98949100 0.30998700 0.39261000 C -0.32811800 0.05375300 -0.37590700 C -1.61301700 0.29979600 0.44898800 F 2.29175800 1.60482400 -1.09853700 F 0.81766000 1.47700100 1.06894700 F 1.13065000 -0.67868100 1.29362200 F -0.36796800 0.86385500 -1.44543200 F -0.32208100 -1.21881000 -0.80580300 F -1.84569500 1.61624800 0.50776500 F -1.45915000 -0.17048200 1.69358500 F 2.99862800 -1.74400600 -0.22231700 H 3.95752400 -0.34313000 -1.35621800 O 5.04261000 -0.26550200 0.69727400 H 5.06462000 0.68489500 0.85028300 C -2.86734500 -0.36896700 -0.15354900 F -3.94628300 0.10658900 0.45211000 F -2.82856800 -1.68095100 0.01806100 F -2.94936700 -0.10117200 -1.45067400 TS23 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1403.428673 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.047464 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.107915 a.u. G = E(DMSO) + Gcorr = -1403.381209 a.u. H = E(DMSO) + Hcorr = -1403.320758 a.u. C 3.31962800 -0.11971700 -0.29628100 C 2.30369300 0.77647100 0.04043600 C 1.05235400 0.42805100 0.70457800 C -0.20399100 0.37431200 -0.21566600 C -1.38657300 -0.42690700 0.38130100 F 2.05688900 1.74325500 -0.94844600 138 F 0.68441900 1.34230000 1.68589200 F 1.13354300 -0.76739200 1.33810000 F -0.63627400 1.62395700 -0.47610200 F 0.10970000 -0.20763500 -1.38349200 F -1.53714000 -0.15534900 1.68522400 F -1.14319500 -1.73705200 0.23731700 F 2.89383200 -1.32401100 -1.40455900 H 4.06286200 0.31643100 -0.96084400 O 3.79950200 -0.90325400 0.71024000 H 4.32637200 -1.60021000 0.29863400 C -2.73973900 -0.13377400 -0.30214000 F -3.62695400 -1.04136600 0.08657400 F -2.61712300 -0.19517300 -1.62207500 F -3.19075200 1.06504200 0.03567000 TS24 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1302.977232 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.033502 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.091771 a.u. G = E(DMSO) + Gcorr = -1302.94373 a.u. H = E(DMSO) + Hcorr = -1302.885461 a.u. C 3.82554900 -0.01249400 -0.40244400 C 2.51451900 0.50175700 -0.06904800 C 1.35412300 -0.18481100 -0.05147800 C -0.00198900 0.48932200 0.00402500 C -1.24718300 -0.37416300 0.38995600 F 2.51724800 1.79699600 0.34179500 F 0.96405700 -0.89317800 1.77842200 F 1.33141400 -1.37791500 -0.61942500 F 0.00922200 1.54711700 0.82358300 F -0.23967000 0.97246400 -1.25299200 F -1.55644800 -0.18937200 1.67678900 F -1.07236900 -1.67794500 0.15534800 H 4.61497300 0.75596500 -0.31531700 O 4.08443200 -1.14614600 -0.74937300 C -2.51546200 0.03708500 -0.39788900 F -2.71213600 1.34837600 -0.31685300 F -2.43906900 -0.31837000 -1.67210100 F -3.56533200 -0.57783800 0.13783100 TS25 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1278.926456 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.042154 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.103303 a.u. 139 G = E(DMSO) + Gcorr = -1278.884302 a.u. H = E(DMSO) + Hcorr = -1278.823153 a.u. C -4.21059700 0.08318200 0.25786800 C -2.02834100 0.01529200 0.08377900 C -0.94069500 0.78017700 0.10932400 C 0.41471800 0.57884400 -0.48496700 C 1.37992900 -0.15999500 0.46399900 F -1.85104900 -1.15368800 -0.62661400 F -0.97892600 1.94611800 0.83061600 F 0.35236900 -0.14222400 -1.62492300 F 0.99112200 1.77079500 -0.78662600 F 0.87657000 -1.37810500 0.71793300 F 1.45594900 0.52770600 1.61628600 H -4.19005300 0.88000200 1.00318600 O -4.57701800 0.23989200 -0.89967000 O -4.36364800 -1.12330100 0.88158900 H -4.48725000 -1.77602400 0.17666200 C 2.82279100 -0.36560400 -0.03391800 F 2.84119100 -1.06092900 -1.16253000 F 3.42996900 0.79621200 -0.23095700 F 3.50233700 -1.04234100 0.88773500 TS26 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1326.914735 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.020814 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.078772 a.u. G = E(DMSO) + Gcorr = -1326.893921 a.u. H = E(DMSO) + Hcorr = -1326.835963 a.u. C 3.60592000 -0.12298600 -0.55430600 C 2.54871600 0.23672500 -0.05364100 C 1.28207700 -0.06174600 0.62605800 C -0.01009700 0.38254700 -0.12303400 C -1.21070200 -0.56166300 0.12994600 F 2.18789900 2.00901900 -0.08717400 F 1.20415900 0.44738600 1.87821700 F 1.20349000 -1.41822500 0.77099200 F -0.39685400 1.60428700 0.27100700 F 0.21502300 0.40137400 -1.44483600 F -1.29283200 -0.85387700 1.43685000 F -1.05154700 -1.69233700 -0.56806300 F 4.43662900 -1.08917600 -0.87211100 C -2.57102200 0.04702600 -0.28267400 140 F -3.48371100 -0.91617900 -0.30679400 F -2.95871900 0.97011100 0.58388200 F -2.49346500 0.59101500 -1.49020300 TS27 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1403.376233 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.045144 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.106635 a.u. G = E(DMSO) + Gcorr = -1403.331089 a.u. H = E(DMSO) + Hcorr = -1403.269598 a.u. C 2.76935500 1.39111200 0.35338600 C 2.36289300 0.12813900 0.45499000 C 1.15858200 -0.42684700 -0.26239100 C -0.15018800 0.19009200 0.29856700 C -1.43575900 -0.56646600 -0.12078800 F 2.63820900 -0.52627500 1.59342300 F 1.02764200 -1.75246200 -0.07534900 F 1.17975500 -0.15354600 -1.57655800 F -0.10158200 0.17739000 1.64200500 F -0.24915200 1.46732200 -0.10604300 F -1.59459200 -1.63260000 0.67335100 F -1.34566500 -0.98354400 -1.39039600 F 2.38097300 2.14727600 -0.70739500 H 3.51611600 1.84590000 0.98642000 C -2.71123600 0.29488700 -0.00269400 F -3.77717000 -0.48681700 -0.10681400 F -2.74061400 0.90633200 1.17518500 F -2.75779000 1.20283700 -0.96517200 O 3.56663200 -1.31986300 -0.69224900 H 4.04882700 -0.64570300 -1.18097400 TS28 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1254.436548 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.042355 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.102135 a.u. G = E(DMSO) + Gcorr = -1254.394193 a.u. H = E(DMSO) + Hcorr = -1254.334413 a.u. C 3.29765300 -1.15580600 0.18540900 C 2.15803000 -0.40054400 0.42682200 C 1.36933400 0.39248600 -0.46138800 141 C -0.07502900 0.73057000 0.00828000 C -0.97489200 -0.53040600 -0.07186400 F 1.78385400 -0.36085600 1.76819100 F -0.22532300 1.18930700 1.26605600 F -0.64128400 1.63257500 -0.82521900 F -0.69666000 -1.34430700 0.96264300 F -0.74923800 -1.20959600 -1.21068800 H 3.66685500 -1.62541500 1.12442500 O 3.91643700 -1.37675800 -0.87619000 O 1.55826400 0.48341300 -1.67588900 O 1.88757400 2.47288300 0.29470300 H 2.35113400 2.54184100 -0.54503700 C -2.49374400 -0.26222400 -0.03070500 F -2.82018900 0.53263100 0.98090900 F -2.91404700 0.29038100 -1.16156400 F -3.13759200 -1.41871000 0.12414800 TS29 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1254.442007 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.045413 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10266 a.u. G = E(DMSO) + Gcorr = -1254.396594 a.u. H = E(DMSO) + Hcorr = -1254.339347 a.u. C C C C C F F F F F H O O O H C F F F TS30 -3.36582900 -2.36581700 -1.06906600 0.05800300 1.24331000 -1.79425000 -0.38199800 0.64914500 0.86058600 2.09311300 -3.19146600 -4.29398600 -0.59359200 -1.61589000 -2.67457700 2.10890700 1.86205700 3.40657700 1.99774200 -0.56023400 0.44288700 -0.42029400 0.72949300 0.53654600 0.83455900 2.00577900 0.80637000 0.62890200 1.58532400 -1.16541100 -0.84757400 -1.41112300 -0.52279600 1.32806100 -0.75514300 -1.64151400 -0.41933000 -1.32789500 -0.63110900 -0.40274000 0.65363900 0.65974300 -0.30923000 -1.63179700 0.41856900 1.89194900 -1.58962600 -0.09908500 -1.54431500 0.11460200 -0.04140000 1.81127900 0.14495000 -0.16133200 -1.11038800 -0.30018100 1.02830200 142 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1254.434562 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.042018 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.10211 a.u. G = E(DMSO) + Gcorr = -1254.392544 a.u. H = E(DMSO) + Hcorr = -1254.332452 a.u. C -2.94947900 -0.83186100 -0.50895000 C -1.79047700 0.00799900 -0.23720500 C -0.82230800 -0.10847600 0.72505300 C 0.35932300 0.89796200 0.64962200 C 1.46716500 0.52158800 -0.35002800 F -1.66427500 1.02111400 -1.17423700 F 0.00777000 2.17295100 0.33295800 F 0.96670700 0.97848000 1.85752200 F 2.50533300 1.37105300 -0.19589800 F 1.01442200 0.65100400 -1.60738600 H -3.30167100 -0.71166200 -1.54613900 O -3.26409700 -1.82909600 0.14974900 O -0.70171500 -0.95439100 1.65018100 C 2.03829900 -0.90181600 -0.22358300 F 2.46299600 -1.14456400 1.00779900 F 1.13978600 -1.81069200 -0.56732700 F 3.07759100 -1.01571500 -1.05205100 O -4.44585200 0.66875800 -0.14247100 H -4.81311800 0.10443800 0.54460400 TS31 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -2028.318027 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.046131 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.122854 a.u. G = E(DMSO) + Gcorr = -2028.271896 a.u. H = E(DMSO) + Hcorr = -2028.195173 a.u. C -4.39319500 0.23205400 -0.39490300 C -3.17431800 -0.43710900 0.27884800 C -1.83542900 0.26559700 -0.05632900 C -0.60919000 -0.64468800 0.20270100 C 0.72273400 0.12654300 0.34367300 F -4.33387600 1.54845100 -0.24010200 F -4.42615600 -0.05339400 -1.68664400 F -5.50334300 -0.21834800 0.16967900 F -3.13005300 -1.71327500 -0.12518400 F -3.36296400 -0.40251300 1.60123700 143 F -1.84727100 0.61869000 -1.34977900 F -1.74932500 1.37453800 0.68855500 F -0.51345400 -1.50260900 -0.82065500 F -0.82055500 -1.34156400 1.33171600 F 0.75790600 1.06039400 -0.63896500 F 0.69439000 0.80684000 1.50868000 O 1.72250000 -0.74704500 0.28102700 C 3.03126900 -0.13706400 0.43209100 F 3.42246700 -0.51526100 1.73993300 C 3.36540000 2.32149000 -0.15069900 O 3.08131200 2.77256400 0.88345000 O 3.70126300 2.16403800 -1.25396000 C 3.88900500 -1.00274200 -0.44275400 F 5.18251900 -0.65295000 -0.32815500 F 3.85534200 -2.33693700 -0.17921500 F 3.55012300 -0.87883500 -1.73331400 TS32 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1839.701735 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.037908 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.107841 a.u. G = E(DMSO) + Gcorr = -1839.663827 a.u. H = E(DMSO) + Hcorr = -1839.593894 a.u. C -4.03551600 -0.41415100 -0.11800400 C -2.78242600 0.33257300 0.39004400 C -1.47811300 -0.11668600 -0.31179900 C -0.21129300 0.27973800 0.48792200 C 1.07061700 0.29725400 -0.37189100 F -4.05642300 -0.41660100 -1.44418900 F -4.04444300 -1.66209600 0.32124700 F -5.11772700 0.20375500 0.33029300 F -2.67984700 0.11680800 1.70754900 F -2.96326300 1.63798900 0.17017600 F -1.49517300 -1.44881800 -0.45181400 F -1.44116600 0.44253000 -1.52725200 F -0.05649100 -0.59963300 1.48302300 F -0.38455600 1.50268900 1.01046700 F 1.08638200 -0.80641900 -1.14123000 F 1.02984300 1.35132800 -1.20086300 O 2.13321100 0.35160700 0.46174100 C 3.34553400 0.51262200 -0.18516000 F 3.77587300 1.79883100 -0.14941400 C 4.26494700 -0.47583700 -0.12867300 144 F 5.42768500 -0.29281800 -0.72165500 F 5.04939500 -0.69049600 1.55127700 F 3.85789100 -1.72659600 -0.18967900 TS33 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1815.633022 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.04642 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.11902 a.u. G = E(DMSO) + Gcorr = -1815.586602 a.u. H = E(DMSO) + Hcorr = -1815.514002 a.u. C -4.03659100 -0.42531600 -0.11705200 C -2.79122200 0.33980100 0.38283300 C -1.47975200 -0.12304100 -0.29666000 C -0.22137600 0.29610300 0.50468300 C 1.06696800 0.28859900 -0.34518600 F -4.04206900 -0.46575600 -1.44278600 F -4.04577300 -1.66012300 0.35775700 F -5.12568700 0.20126900 0.30087900 F -2.69804100 0.15854300 1.70610700 F -2.97426900 1.63823700 0.12776900 F -1.49090300 -1.45785800 -0.40454700 F -1.43081900 0.40725000 -1.52445200 F -0.07196900 -0.55502300 1.52383400 F -0.39679300 1.53297900 0.98971800 F 1.10264000 -0.83901900 -1.07249100 F 1.04208100 1.31378300 -1.20624400 O 2.12482300 0.37364900 0.50369800 C 3.33640800 0.52545200 -0.11352000 F 3.71957200 1.79892700 -0.25531400 C 4.17856500 -0.47239300 -0.30263000 F 5.32636300 -0.30848700 -0.91097000 F 3.81089700 -1.72566500 -0.21967800 O 5.26455600 -0.59648300 1.75651000 H 6.03990500 -1.14406400 1.91729300 TS34 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1815.694019 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.049543 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.120059 a.u. G = E(DMSO) + Gcorr = -1815.644476 a.u. H = E(DMSO) + Hcorr = -1815.57396 a.u. 145 C -4.04779700 -0.36684300 -0.15750000 C -2.77170800 0.20803500 0.49579300 C -1.50007800 -0.00443400 -0.36236900 C -0.20089100 0.12190700 0.47151700 C 1.05981100 0.38251700 -0.38046800 F -4.11162700 0.00072900 -1.43049800 F -4.05476400 -1.68799800 -0.08421900 F -5.10936400 0.10199700 0.48057700 F -2.61679100 -0.38338500 1.68686100 F -2.95530000 1.51897000 0.67726800 F -1.54357800 -1.22744300 -0.90871400 F -1.50289000 0.90441600 -1.34489700 F -0.03686600 -1.01763400 1.15331200 F -0.34057000 1.13333500 1.34255200 F 1.03330300 -0.45526500 -1.43639400 F 0.99641000 1.63104700 -0.87933800 O 2.13434500 0.20178700 0.40370900 C 3.35043200 0.51660700 -0.20997400 F 3.75718400 1.76612100 0.19435800 C 4.31688600 -0.46255700 -0.18032000 F 4.87659800 -0.91244300 1.47041500 F 5.53236800 -0.04947000 -0.57492000 O 3.99805600 -1.70038200 -0.56392400 H 4.38384500 -2.28939700 0.10438600 TS35 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1791.667119 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.061139 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.132465 a.u. G = E(DMSO) + Gcorr = -1791.60598 a.u. H = E(DMSO) + Hcorr = -1791.534654 a.u. C -4.05217100 -0.42067700 -0.07234500 C -2.79349800 0.36393800 0.35898400 C -1.49819600 -0.14058000 -0.32304800 C -0.22179200 0.30575900 0.43303200 C 1.06254300 0.24453700 -0.42222700 F -4.08106100 -0.54365700 -1.39270100 F -4.06260100 -1.62396900 0.47829300 F -5.13048400 0.23883900 0.32329600 F -2.67601800 0.25394700 1.68848500 F -2.97874900 1.64783700 0.03850800 F -1.52522800 -1.47988200 -0.36725400 F -1.47621800 0.32907700 -1.57605300 F -0.07236200 -0.49578400 1.49513200 146 F -0.38813300 1.56663200 0.86140400 F 1.06933900 -0.94085800 -1.07288800 F 1.00227200 1.20110400 -1.36511800 O 2.11329200 0.39207800 0.39591300 C 3.36528500 0.45899700 -0.27938500 F 3.72945300 1.79779900 -0.33733100 C 4.33953700 -0.34509800 0.35838800 F 5.17132900 -1.34134000 -0.98460300 O 3.95471800 -1.38997300 1.09633600 H 3.06049800 -1.65615100 0.83729400 O 5.47352200 0.22573700 0.75760300 H 6.16315900 -0.45554700 0.74095400 TS36 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1767.684371 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.069563 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.140758 a.u. G = E(DMSO) + Gcorr = -1767.614808 a.u. H = E(DMSO) + Hcorr = -1767.543613 a.u. C -3.90941700 0.17972700 -0.42937500 C -2.68932700 -0.32777100 0.37072400 C -1.34795400 0.26630900 -0.12665400 C -0.12672900 -0.57042000 0.32950600 C 1.21590200 0.19244900 0.26652200 F -3.84754100 1.49768000 -0.56674600 F -3.94747000 -0.38187000 -1.62708400 F -5.01761700 -0.13394300 0.22466400 F -2.65885200 -1.66282000 0.27124100 F -2.86541200 0.01257200 1.65090000 F -1.36430100 0.30844100 -1.46652600 F -1.24889500 1.51708000 0.33949800 F -0.05163200 -1.64835800 -0.46046100 F -0.32571300 -0.97313000 1.59463600 F 1.26559000 0.83757400 -0.92507300 F 1.20988500 1.15270400 1.21042600 O 2.20280200 -0.69709200 0.41967000 C 3.56805700 -0.23810300 0.55490800 F 3.67274700 0.33733200 1.81033700 C 3.91457200 0.79798600 -0.49280000 O 4.10686500 0.25673400 -1.69365200 H 4.23657100 -0.74060700 -1.57471700 O 4.63328100 -2.10661800 -0.81239800 H 4.25680800 -1.39766700 0.05772600 H 4.00531000 -2.83243800 -0.88764300 147 O 4.10250100 1.97201300 -0.28045300 TS37 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1767.18454 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.059671 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.131506 a.u. G = E(DMSO) + Gcorr = -1767.124869 a.u. H = E(DMSO) + Hcorr = -1767.053034 a.u. C -4.07189600 -0.26333400 0.00627800 C -2.76368300 0.55417600 -0.08191700 C -1.49128700 -0.32925200 -0.08055500 C -0.21492100 0.46166800 0.29673200 C 1.12072300 -0.20142100 -0.12552400 F -4.03652400 -1.28043900 -0.84514200 F -4.25031000 -0.72907000 1.23224900 F -5.09445600 0.52066700 -0.30404500 F -2.73841800 1.39590100 0.96016200 F -2.80000500 1.26317500 -1.21520600 F -1.66638100 -1.32254900 0.80588600 F -1.36648100 -0.86574400 -1.30121500 F -0.22456000 0.62032100 1.62946200 F -0.28804200 1.68044600 -0.27281200 F 0.97361500 -1.55863600 0.13870100 F 1.15540600 -0.15176400 -1.50787800 O 2.12741900 0.34146100 0.44688300 C 3.66416200 -0.44252300 0.09152700 H 3.34157100 -1.02099600 -0.75331000 F 3.75094100 -1.10556400 1.23919900 C 4.46260300 0.85338500 -0.06608300 O 4.92434300 1.34055700 0.97872100 O 4.50246000 1.28912300 -1.23421200 O 5.44498900 -1.48349900 -0.59467900 H 5.69747700 -0.87703200 -1.29740100 TS38 E(DMSO)[M06-2X/6-311++G(2d,p), SMD (DMSO)] = -1767.149035 a.u. Gcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.062824 a.u. Hcorr(DMSO)[M06-2X/6-311++G(2d,p)] = 0.132234 a.u. G = E(DMSO) + Gcorr = -1767.086211 a.u. H = E(DMSO) + Hcorr = -1767.016801 a.u. C -3.11871500 -1.11399600 0.10349100 148 C -2.33131800 0.19477700 -0.13981300 C -0.78212500 -0.01958500 -0.07919900 C -0.03320200 1.31969400 0.20752200 C 1.52078700 1.45717800 0.05892600 F -2.60450700 -2.10867300 -0.60875100 F -3.10701200 -1.44585800 1.38562300 F -4.38090200 -0.93397600 -0.26879100 F -2.75321400 1.07967100 0.77390800 F -2.68012300 0.63911900 -1.35461000 F -0.57137900 -0.93016800 0.88158000 F -0.45858500 -0.52251400 -1.27750100 F -0.34590000 1.63700400 1.47559400 F -0.66378000 2.16192300 -0.64744600 F 2.05003000 1.64007500 -1.17432600 F 2.30322600 1.52898500 1.15906800 O 1.72284100 -0.22639700 -0.00044300 C 2.94470600 -0.67121300 -0.33653100 H 3.74176400 0.05414100 -0.14420400 F 3.01144300 -0.88003400 -1.75583600 C 3.25497400 -2.01203600 0.37258900 O 3.95407100 -1.89189300 1.40314900 O 2.76698000 -3.04840200 -0.11600400 O 1.34368500 3.24565100 0.25248300 H 1.03331200 3.59527600 -0.58778600 149 References and Notes 1. A. Leeson, T. Thompson, H. F. Stroo, R. H. 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