Journal
DALTON TRANSACTIONS
Volume 44, Issue 16, Pages 7634-7642Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt00809c
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Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- NRF of Korea through GRL [NRF-2010-00353]
- JST, Japan
- Department of Science and Technology (DST), New Delhi, India [SR/FT/CS-006/2010]
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A mononuclear high-valent trans-dioxoruthenium(VI) complex, trans-[Ru-VI(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-[Ru-VI(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-[Ru-VI(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[ Ru-VI(TMC)(O)(2)](2+) and p-chloranil (Cl(4)Q) and a large kinetic isotope effect (KIE) value of 13(1). In the case of the oxidation of alkyl hydrocarbons by the trans-[Ru-VI(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-d(2) 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.
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