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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(VI) complex
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Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(VI) complex

机译：通过机械原理了解反式二氧六环（VI）配合物氢化物转移与氢原子转移的反应

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摘要

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.
机译：单核高价反式二恶英（VI）络合物，反式-[Ru-VI（TMC）（O）（2）]（2+）（TMC = 1,4,8,11-四甲基-1,4，合成了8,11-四氮杂环十四烷），并通过各种光谱技术和X射线晶体学对其进行了表征。在氢化物转移和氢原子转移反应中研究了反式-[Ru-VI（TMC）（O）（2）]（2+）配合物的反应性。氢化物从二氢神经酰胺酰胺腺嘌呤二核苷酸（NADH）类似物转移到反式[Ru-VI（TMC）（O）（2）]（2+）的机理，该过程通过质子偶联电子转移（PCET）进行，通过观察反式[Ru-VI（TMC）（O）（2）]（2+）和对氯苯醌（Cl的对数速率常数之间的良好线性相关性，已提出了快速电子转移（ET） （4）Q）和13（1）的大动力学同位素效应（KIE）值。在反式-[Ru-VI（TMC）（O）（2）]（2+）配合物氧化烷基烃的情况下，二级速率常数取决于CH键的解离能（BDE）的底物，通过反[RuVI（TMC）（O）（2）]（2+）络合物氧化the吨和氘代x吨-d（2）时，获得的大KIE值为26（2），表明在速率确定步骤中烷基烃的CH键活化通过H原子提取进行。

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