Table3.
ligand | ΔG‡exp | ΔG‡DFT | EHOMOb | Vbur%c | ΔEdist(TS)d | ΔEdist(BrCuIIL)e |
---|---|---|---|---|---|---|
N[2,3,2] | 21.5 | 27.5 | −7.12 | 48.4 | 11.9 | 14.4 |
N[2,2,2] | 18.6 | 26.4 | −7.26 | 45.6 | 14.2 | 17.0 |
Me4Cyclam | 17.7 | 20.3 | −6.92 | 49.6 | 7.0 | 9.0 |
Cyclam-B | 13.6 | 16.8 | −6.81 | 47.6 | 4.0 | 5.2 |
kact values are in M−1 s−1. All free energies and distortion energies are in kcal/mol; EHOMO is in eV. All energies and EHOMO are computed in acetonitrile using the CPCM solvation model.
HOMO energy of [CuIL]+.
Percent buried volume of the ligand computed from the DFT-optimized geometries of [CuIL]+.41
Distortion energy of the CuL catalyst in the ISET transition state with respect to the ground state [CuIL]+.
Distortion energy of the CuL catalyst in the [BrCuIIL]+ complex with respect to the ground state [CuIL]+.