A Bioinspired Disulfide/Dithiol Redox Switch In A Rhenium Complex As Proton, H Atom, And Hydride Transfer Reagent
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY(2021)
摘要
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 center dot center dot center dot S- moiety in the backbone. The disulfide bond in fac-[Re((S-S)bpy)(CO)(3)Cl] (1, (S-S)bpy = [1,2]-dithiino[4,3-b:5,6-b']dipyridine) undergoes two successive reductions at equal potentials of -1.16 V vs Fc(+vertical bar 0) at room temperature forming [Re((S2)bpy)(CO)(3)Cl](2-) (1(2-), (S2)bpy = [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 center dot center dot center dot S- unit, 1H(-). The disulfide/dithiol switch exhibits a rich PCET reactivity and can release a proton (Delta G degrees(+)(H) = 34 kcal mol(-1), pK(a) = 24.7), an H atom (Delta G degrees(center dot)(H) = 59 kcal mol-1), or a hydride ion (Delta G degrees(-)(H) = 60 kcal mol(-1)) as demonstrated in the reactivity with various organic test substrates.
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关键词
Proton-Coupled Electron Transfer,Dioxygen Activation
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