Connor Gannon P, Lease Nicholas, Casuras Andrea, Goldman Alan S, Holland Patrick L, Mayer James M
Department of Chemistry, Yale University, New Haven, Connecticut 06511, USA.
Dalton Trans. 2017 Oct 24;46(41):14325-14330. doi: 10.1039/c7dt03476h.
Protonation and reduction of pincer-ligated Rh- and Ir-N complexes have been studied by NMR spectroscopy and cyclic voltammetry to assess the capability of these complexes to activate or reduce N. Protonation, which is a prerequisite to electrochemical reduction, results in a cationic metal-hydride that loses N under an atmosphere of Ar. Reduction of the metal-hydride results in fast disproportionation of an unobserved transient Ir species. These studies suggest that the regioselectivity of initial protonation is a strong determinant for the ability of a system to facilitate the reduction of N.
通过核磁共振光谱和循环伏安法研究了钳形配位的铑和铱氮配合物的质子化和还原过程，以评估这些配合物活化或还原氮的能力。质子化是电化学还原的先决条件，会生成一种阳离子金属氢化物，该氢化物在氩气氛围下会失去氮。金属氢化物的还原会导致一种未观察到的瞬态铱物种快速歧化。这些研究表明，初始质子化的区域选择性是系统促进氮还原能力的一个重要决定因素。
