A Bioinspired Disulfide/Dithiol Redox Switch in a Rhenium Complex as Proton, H Atom, and Hydride Transfer Reagent

The transfer of multiple electrons and protons is of crucial importance in many reactions relevant in biology and chemistry. Natural redox-active cofactors are capable of storing and releasing electrons and protons under relatively mild conditions and thus serve as blueprints for synthetic proton-coupled electron transfer (PCET) reagents. Inspired by the prominence of the 2e^-/2H⁺ disulfide/dithiol couple in biology, we investigate herein the diverse PCET reactivity of a Re complex equipped with a bipyridine ligand featuring a unique SH···^-S moiety in the backbone. The disulfide bond in fac-[Re(^S-Sbpy)(CO)₃Cl] (1, ^S-Sbpy = [1,2]dithiino[4,3-b:5,6-b']dipyridine) undergoes two successive reductions at equal potentials of -1.16 V vs Fc^+|0 at room temperature forming [Re(^S2bpy)(CO)₃Cl]^2- (1^2-, ^S2bpy = [2,2'-bipyridine]-3,3'-bis(thiolate)). 1^2- has two adjacent thiolate functions at the bpy periphery, which can be protonated forming the S-H···^-S unit, 1H^-. The disulfide/dithiol switch exhibits a rich PCET reactivity and can release a proton (ΔG°_H = 34 kcal mol^-1, pK_a = 24.7), an H atom (ΔG°_H = 59 kcal mol^-1), or a hydride ion (ΔG°_H = 60 kcal mol^-1) as demonstrated in the reactivity with various organic test substrates.