Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(<scp>vi</scp>) complex
作者:Sunder N. Dhuri、Yong-Min Lee、Mi Sook Seo、Jaeheung Cho、Dattaprasad D. Narulkar、Shunichi Fukuzumi、Wonwoo Nam
DOI:10.1039/c5dt00809c
日期:——
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
单核高价反式-二氧杂钌(VI)络合物,反式-[Ru VI(TMC)(O)2 ] 2+(TMC = 1,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷),通过各种光谱技术和X射线晶体学合成并表征。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。氢化物从二氢烟碱酰胺腺嘌呤二核苷酸(NADH)类似物转移至反式-[Ru VI(TMC)(O)2 ]的机理通过观察反式-[Ru VI(TMC)的对数速率常数之间的良好线性相关性,提出了通过质子耦合电子转移(PCET),然后进行快速电子转移(ET)进行的2+)(O) 2 ] 2+和对氯腈(Cl 4 Q),大的动态同位素效应(KIE)值为13(1)。在烷基烃被反式-[Ru VI(TMC)(O) 2 ] 2+氧化的情况下复杂的,二阶速率常数分别为依赖于C-H键离解能的基板(BDE),和26大的KIE值(