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An Isolated Nitridyl Radical‐Bridged {Rh(N . )Rh} Complex
Author(s) -
Gloaguen Yann,
Rebreyend Christophe,
Lutz Martin,
Kumar Pravin,
Huber Martina,
van der Vlugt Jarl Ivar,
Schneider Sven,
de Bruin Bas
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403445
Subject(s) - chemistry , deprotonation , methylene , rhodium , crystallography , stereochemistry , photochemistry , medicinal chemistry , catalysis , organic chemistry , ion
Photochemical activation of [(PNN H )Rh(N 3 )] (PNN H =6‐di‐( tert ‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)RhN . ‐Rh(PNN)] complex 3 (PNN − =methylene‐deprotonated PNN H ), 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.