An Isolated Nitridyl Radical-bridged {Rh(N·)Rh} Complex

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2014 May 21

PMID 24842721

Citations 13

Authors

Yann Gloaguen

Christophe Rebreyend

Martin Lutz

Pravin Kumar

Martina Huber

Jarl Ivar van der Vlugt

Sven Schneider

Bas de Bruin

Affiliations

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Abstract

Photochemical activation of [(PNNH)Rh(N3)] (PNNH = 6-di-(tert-butyl)phosphinomethyl-2,2'-bipyridine) complex 2 produced the paramagnetic (S = 1/2), [(PNN)Rh=N(·)-Rh(PNN)] complex 3 (PNN(-) = methylene-deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical ((·)N(2-)) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)Rh(I)(CO)] complex 4, presumably by nitridyl radical N,N-coupling.

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