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. Author manuscript; available in PMC: 2021 Aug 12.
Published in final edited form as: J Am Chem Soc. 2020 Jul 30;142(32):13917–13933. doi: 10.1021/jacs.0c06243

Table 1.

Comparison of Relative Free Energy Barrier Heights along Reductive Elimination Pathwaysa

Intermediate PhMe Et2O THF DMF
(Re)-13 0.6 0.5 0.5 0.4
(Si)-13 0.0 0.0 0.0 0.0
14 8.8 9.3 9.5 9.8
15 + 17 33.2 17.5 9.2 −0.5
(Re)-TS21 13.5 13.5 13.5 13.6
(Si)-TS21 14.1 14.1 14.1 14.1
(Si/chair)-TS20 9.5 10.3 10.8 11.5
(Re/boat)-TS20 10.9 11.7 12.1 12.7
(endo/Si/t-P)-TS22 14.9b 13.9b 13.3 12.6
(exo/Re/t-N)-TS22 16.0b 14.7b 13.9 12.9
(endo/Si/t-P)-TS23 19.8 17.8 16.6 15.1
(endo/Re/t-P)-TS23 19.1 17.2 16.1 14.8
a

Relative free energies given in kcal/mol at the M06/def2-TZVP–CPCM(solvent) level of theory on geometries obtained in the gas phase.

b

Barrier less than free energy of separated ions (exo)-15 and 17.