Hydride-Transfer Reaction to a Mononuclear Manganese(III) Iodosylarene Complex

Abstract

Metal iodosylarene species have received interest because of their potential oxidative power as a catalyst. We present the first example of hydride-transfer reactions to a mononuclear manganese(III) iodosylbenzene complex, [Mn-III(TBDAP)(OIPh)-(OH)](2+) (1; TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane), with dihydronicotinamide adenine dinucleotide (NADH) analogues. Kinetic studies show that hydride-transfer from the NADH analogues to 1 occurs via a proton-coupled electron transfer, followed by a rapid electron transfer.