Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(vi) complex

Sunder N. Dhuri, Yong Min Lee, Mi Sook Seo, Jaeheung Cho, Dattaprasad D. Narulkar, Shunichi Fukuzumi, Wonwoo Nam

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Abstract

A mononuclear high-valent trans-dioxoruthenium(vi) complex, trans-[RuVI(TMC)(O)2]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was synthesized and characterized by various spectroscopic techniques and X-ray crystallography. The reactivity of the trans-[RuVI(TMC)(O)2]2+ complex was investigated in hydride transfer and hydrogen atom transfer reactions. The mechanism of hydride transfer from dihydronicotinamide adenine dinucleotide (NADH) analogues to trans-[RuVI(TMC)(O)2]2+, which proceeds via a proton-coupled electron transfer (PCET), followed by a rapid electron transfer (ET), has been proposed by the observation of a good linear correlation between the log rate constants of trans-[RuVI(TMC)(O)2]2+ and p-chloranil (Cl4Q) and a large kinetic isotope effect (KIE) value of 13(1). In the case of the oxidation of alkyl hydrocarbons by the trans-[RuVI(TMC)(O)2]2+ complex, the second-order rate constants were dependent on the C-H bond dissociation energy (BDE) of the substrates, and a large KIE value of 26(2) was obtained in the oxidation of xanthene and deuterated xanthene-d2 by the trans-[RuVI(TMC)(O)2]2+ complex, indicating that the C-H bond activation of alkyl hydrocarbons proceeds via an H-atom abstraction in the rate-determining step.

Original languageEnglish
Pages (from-to)7634-7642
Number of pages9
JournalDalton Transactions
Volume44
Issue number16
DOIs
StatePublished - 28 Apr 2015

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