Scheme 3. Electrochemical and Electrocatalytic Results.

(A) (a) Electrolysis with 1 (from ref (32)) or 4 as a Precatalyst. Yields, F.E., and Z/E Ratios Are Reported at Full Conversion; TOF_exp Values Are Estimated Based on Time to Full Conversion; (b) CVs of 3 Alone (Dotted Blue, Oxidation First), 4 Alone (Black), with S1 (10 equiv) (Blue), or with S1 and BzOH (50 equiv) (red); and (c) Experimental and Computed Redox Potentials (V vs Fc^+/0) for Compounds 3 and 4; (B) CVs of Mixtures of 4, S1, and BzOH; (a) Increasing [S1] from 5 to 50 mM (Light to Dark Green) and Plot of log(TOF_MAX) with Respect to log([S1]); (b) Increasing [BzOH] from 5 to 50 mM (Light to Dark Blue) and Plot of log(TOF_MAX) with Respect to log([BzOH]); (c) Increasing [4] from 0.5 to 4 mM (Light to Dark Red) and Plot of log(TOF_MAX) with Respect to log([4]); and (d) with BzOD (Purple) or BzOH (Blue); Conditions for Electrolysis: [Catalyst] = 1 mM, [S1] = 10 mM, [BzOH] = 100 mM, E_app = −1.72 ± 0.02 V_Fc; Conditions for CV: Unless Otherwise Stated [4] = 1 mM, [S1] = 10 mM, [BzOH] = 50 mM, 0.1 V·s^–1 as Scan Rate (ν); Supporting Electrolyte: DMF 0.1 M nBu₄NPF₆. ^bE_p,a. ^cE_1/2. ^dE_p,c. ^eE°. ^fQuadruplet Configuration (See SI Section 5.2 for Other Spin Configurations). ^gAfter the Release of One Benzoate Ligand (See Scheme S1).