Table2.

Steric effects of the TREN family ligands.^a

ligand	ΔG‡exp	ΔG‡DFT	EHOMOb	Vbur%c	ΔEdist(TS)d	ΔEdist(BrCuIIL)e
Et6TREN	19.3	18.5	−7.33	56.5	3.5	5.1
Me6TREN	13.8	14.3	−7.34	45.7	2.2	4.0

^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 geometries 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]⁺.