从二氢化铱中损失氢化物的电化学和化学途径。

Electrochemical and chemical routes to hydride loss from an iridium dihydride.

作者信息

Walden A G, Kumar A, Lease N, Goldman A S, Miller A J M

机构信息

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA.

Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA and Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati - 781039, Assam, India.

出版信息

Dalton Trans. 2016 Jun 14;45(24):9766-9. doi: 10.1039/c6dt00522e.

DOI:10.1039/c6dt00522e

PMID:26979786

Abstract

With a view towards replacing sacrificial hydrogen acceptors in alkane dehydrogenation catalysis, electrochemical methods for oxidative activation of a pincer-ligated iridium hydride intermediate were explored. A 1H(+)/2e(-) oxidation process was observed in THF solvent, with net hydride loss leading to a reactive cationic intermediate that can be trapped by chloride. Analogous reactivity was observed with the concerted hydride transfer reagent Ph3C(+), connecting chemical and electrochemical hydride loss pathways.

摘要

为了在烷烃脱氢催化中替代牺牲性氢受体，人们探索了用于氧化活化钳形配位氢化铱中间体的电化学方法。在四氢呋喃溶剂中观察到一个1H(+)/2e(-)氧化过程，净氢化物损失导致生成一种活性阳离子中间体，该中间体可被氯离子捕获。使用协同氢化物转移试剂三苯基碳正离子（Ph3C(+)）时观察到了类似的反应活性，这将化学和电化学氢化物损失途径联系了起来。