An Isolated Nitridyl Radical‐Bridged {Rh(N.)Rh} Complex1. Issue 26 (19th May 2014)

• Record Type: Journal Article
• Authors: Gloaguen, Yann; Rebreyend, Christophe; Lutz, Martin; Kumar, Pravin; Huber, Martina; van der Vlugt, Jarl Ivar; Schneider, Sven; de Bruin, Bas
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 26(2014)
• Page Start: 6814
• Page End: 6818
• Publication Date: 2014-05-19
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201403445
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Photochemical activation of [(PNN<italic>H</italic>)Rh(N₃)] (PNN<italic>H</italic>=6‐di‐(<italic>tert</italic>‐butyl)phosphinomethyl‐2, 2′‐bipyridine) complex <bold>2</bold> produced the paramagnetic (S=1/2), [(PNN)RhN^.‐Rh(PNN)] complex <bold>3</bold> (PNN⁻=methylene‐deprotonated PNN<italic>H</italic>), which could be crystallographically characterized. Spectroscopic investigation of <bold>3</bold> indicates a predominant nitridyl radical (^.N²⁻) character, which was confirmed computationally. Complex <bold>3</bold> reacts selectively with CO, producing two equivalents of [(PNN)Rh^I(CO)] complex <bold>4</bold>, presumably by nitridyl radical N, N‐coupling.</p> </abstract>