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Table 1.a Calculated relative free energies (kcal mol-1) for various models for the reaction between 4 and carbon dioxide.
aViewing the table requires a Javascript-enabled Web browser. Coordinates are provided for all stationary points upon clicking a hyperlink, and an animation of selected normal modes is available for transition states with displacement vectors for each mode shown in yellow. To animate any other of the 3N-6 normal vibrational modes, right click with the mouse in the viewing area and select another entry from the model list available from the top menu item (shown as e.g. model 28/53, where the 28th model is currently showing out of a total of 53 available). Calculations involve models at the gas phase or the self-consistent-reaction-field (SCRF/CPCM) level for solvent=water. Each entry is also linked to an OAI-PMH compliant institutional data repository shown as dr, which provides access to full information about each system. Information includes the total calculated energies via Gaussian checkpoint, logfile and CML coordinate files. Metadata conforms to the METS specifications. bB3LYP/6-311G(d,p)@298K cωB97XD/6-311G(d,p)@298K dωB97XD/6-311G(d,p)@175K eTriplet state fAutomerization isomer 3 gReported crystal structure, retrieved using www.ccdc.cam.ac.uk/data_request/cif and reference code 764868 with DOI: 10.5517/cctnx5j hTransition state for C-O bond formation from intermediate zwitterion. iIntermediate zwitterion. jReported crystal structure, retrieved using www.ccdc.cam.ac.uk/data_request/cif and reference code 764866 and DOI: 10.5517/cctnx3g. kQTAIM analysis, showing bond critical points in purple, ring critical points in yellow and cage critical points in green. Bond paths are based purely on distance. lValues, at 175K for model F, which is E with an additional two explicit water molecules added. m Model for Diels-Alder reaction reported in DOI: 10.1021/ja964198s.
Model ΔG4 + CO2, ΔGTS(4 + CO2 → 2)
[-T.ΔS4 + CO2 → 2]
ΔGreaction (4 + CO2 → 2)
[-T.ΔSreaction (4 + CO2 → 2)]
A 0.0 b,dr,dr, 0.0 c,dr,dr, 0.0 d,dr,dr 22.2 b,dr, 20.9 c,dr, 16.8 d,dr [+5.75]d +2.2 b,dr, -6.4 c,dr, -16.8 d,dr [+6.71]d
B 0.0 b,dr,dr, 0.0 c,dr,dr, 0.0 d,dr,dr 17.6 b,dr, 17.0 c,dr, 12.9 d,dr [+5.71]d -0.4 b,dr, -8.5 c,dr, -13.4 d,dr [+6.74]d
C 0.0 b,dr,dr, 0.0 c,dr,dr, 0.0 d,dr,dr 7.5 b,dr, 8.5 c,dr, 3.3 d,dr [+7.4]d -18.1 b,dr, -23.9 c,dr, -30.6 d,dr [+9.32]d
D 0.0 b,dr,dr, 0.0 c,dr,dr, 0.0 d,dr,dr 16.6 b,dr, 14.1 c,dr, 9.2 d,dr [+7.13]d
-3.7 c,h,dr, -10.3 d,h,dr [+7.13]d
-1.7 b,dr, -6.1 c,dr, -11.9 d,dr
-6.5 b,dr, -12.7 c,dr, -19.6 d,dr [+9.65]d
E 0.0 b,dr, 0.0 c,dr, 0.0 d,dr,
10.3 e,dr, 0.3 f,dr, X-Ray g
7.6 b,dr, 8.9 c,dr, 8.0 d,dr [+1.12]d
10.5 [2.04]l,dr,dr, AIM k
-14.6 c,h,dr, -19.7 d,h,dr[3.59]
-18.0 c,i,dr, -19.8 d,i,dr [+2.28]d
-11.6 b,dr, -26.3 c,dr, -29.0 d,dr [+2.75]d
X-Ray j