A Mononuclear Non-Heme Manganese(III)-Aqua Complex in Oxygen Atom Transfer Reactions via Electron Transfer

Metal-oxygen complexes, such as metal-oxo [M(O^2-)], -hydroxo [M(OH^-)], -peroxo [M(O₂^2-)], -hydroperoxo [M(OOH^-)], and -superoxo [M(O₂^•-)] species, are capable of conducting oxygen atom transfer (OAT) reactions with organic substrates, such as thioanisole (PhSMe) and triphenylphosphine (Ph₃P). However, OAT of metal-aqua complexes, [M(OH₂)]ⁿ⁺, has yet to be reported. We report herein OAT of a mononuclear non-heme Mn(III)-aqua complex, [(dpaq)Mn^III(OH₂)]²⁺ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), to PhSMe and Ph₃P derivatives for the first time; it is noted that no OAT occurs from the corresponding Mn(III)-hydroxo complex, [(dpaq)Mn^III(OH)]⁺ (2), to the substrates. Mechanistic studies reveal that OAT reaction of 1 occurs via electron transfer from 4-methoxythioanisole to 1 to produce the 4-methoxythioanisole radical cation and [(dpaq)Mn^II(OH₂)]⁺, followed by nucleophilic attack of H₂O in [(dpaq)Mn^II(OH₂)]⁺ to the 4-methoxythioanisole radical cation to produce an OH adduct radical, 2,4-(MeO)₂C₆H₃S^•(OH)Me, which disproportionates or undergoes electron transfer to 1 to yield methyl 4-methoxyphenyl sulfoxide. Formation of the thioanisole radical cation derivatives is detected by the stopped-flow transient absorption measurements in OAT from 1 to 2,4-dimethoxythioanisole and 3,4-dimethoxythioanisole, being compared with that in the photoinduced electron transfer oxidation of PhSMe derivatives, which are detected by laser-induced transient absorption measurements. Similarly, OAT from 1 to Ph₃P occurs via electron transfer from Ph₃P to 1, and the proton effect on the reaction rate has been discussed. The rate constants of electron transfer from electron donors, including PhSMe and Ph₃P derivatives, to 1 are fitted well by the electron transfer driving force dependence of the rate constants predicted by the Marcus theory of outer-sphere electron transfer.