Skip to main content
. Author manuscript; available in PMC: 2020 May 8.
Published in final edited form as: J Am Chem Soc. 2019 Apr 29;141(18):7486–7497. doi: 10.1021/jacs.9b02158

Table3.

Flexibility effects of the Cyclam family ligands.

graphic file with name nihms-1039010-t0016.jpg
ligand ΔGexp ΔGDFT 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
a

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.

b

HOMO energy of [CuIL]+.

c

Percent buried volume of the ligand computed from the DFT-optimized geometries of [CuIL]+.41

d

Distortion energy of the CuL catalyst in the ISET transition state with respect to the ground state [CuIL]+.

e

Distortion energy of the CuL catalyst in the [BrCuIIL]+ complex with respect to the ground state [CuIL]+.