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

doi:10.1039/c5dt00809c

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

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 (Cl₄Q) 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-d₂ by the trans-[Ru^VI(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 language	English
Pages (from-to)	7634-7642
Number of pages	9
Journal	Dalton Transactions
Volume	44
Issue number	16
DOIs	https://doi.org/10.1039/c5dt00809c
State	Published - 28 Apr 2015

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© The Royal Society of Chemistry 2015.

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10.1039/c5dt00809c

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@article{ffdb25a372b44725baec9ea81750000d,

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

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.",

author = "Dhuri, \{Sunder N.\} and Lee, \{Yong Min\} and Seo, \{Mi Sook\} and Jaeheung Cho and Narulkar, \{Dattaprasad D.\} and Shunichi Fukuzumi and Wonwoo Nam",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2015.",

year = "2015",

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doi = "10.1039/c5dt00809c",

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volume = "44",

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T1 - Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(vi) complex

AU - Dhuri, Sunder N.

AU - Lee, Yong Min

AU - Seo, Mi Sook

AU - Cho, Jaeheung

AU - Narulkar, Dattaprasad D.

AU - Fukuzumi, Shunichi

AU - Nam, Wonwoo

PY - 2015/4/28

Y1 - 2015/4/28

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/84927925669

U2 - 10.1039/c5dt00809c

DO - 10.1039/c5dt00809c

M3 - Article

C2 - 25811701

AN - SCOPUS:84927925669

SN - 1477-9226

VL - 44

SP - 7634

EP - 7642

JO - Dalton Transactions

JF - Dalton Transactions

IS - 16

ER -

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

Abstract

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