Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(vi) complex
- 등재 SCIE, SCOPUS
- 발행기관 Royal Society of Chemistry
- 발행년도 2015
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000115375
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/c5dt00809c
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
A mononuclear high-valent trans-dioxoruthenium(vi) complex, trans-[RuVI(TMC)(O)<inf>2</inf>]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)<inf>2</inf>]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)<inf>2</inf>]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)<inf>2</inf>]2+ and p-chloranil (Cl<inf>4</inf>Q) 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)<inf>2</inf>]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<inf>2</inf> by the trans-[RuVI(TMC)(O)<inf>2</inf>]2+ complex, indicating that the C-H bond activation of alkyl hydrocarbons proceeds via an H-atom abstraction in the rate-determining step. © The Royal Society of Chemistry 2015.
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