Table1.

Electronic effects of the TPMA family ligands.^a

ligand	ΔG‡exp	ΔG‡DFT	EHOMOb	Vbur%c	ΔEdist(TS)d	ΔEdist(BrCuIIL)e
TPMA	15.0	16.6	−7.66	39.2	2.1	4.0
TPMA*3	12.0	14.6	−7.41	40.3	2.0	3.6
TPMANMe2	10.0	13.0	−7.36	39.0	1.8	3.7

^ak_act values are in M⁻¹ s⁻¹. All Gibbs free energies and distortion energies are in kcal/mol; E_HOMO is in eV. All energies and E_HOMO are computed in acetonitrile using the CPCM solvation model.

^bHOMO energy of [Cu^IL]⁺.

^cPercent buried volume of the ligand computed from the DFT-optimized geometry of [Cu^IL]⁺.⁴¹

^dDistortion energy of the CuL catalyst in the ISET transition state with respect to the ground state [Cu^IL]⁺.

^eDistortion energy of the CuL catalyst in the [BrCu^IIL]⁺ complex with respect to the ground state [Cu^IL]⁺.