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An Isolable Terminal Imido Complex of Palladium and Catalytic Implications
Author(s) -
Grünwald Annette,
Orth Nicole,
Scheurer Andreas,
Heinemann Frank W.,
Pöthig Alexander,
Munz Dominik
Publication year - 2018
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.201809152
Subject(s) - nitrene , reactivity (psychology) , chemistry , palladium , valency , catalysis , antibonding molecular orbital , population , stereochemistry , medicinal chemistry , organic chemistry , physics , atomic orbital , medicine , linguistics , philosophy , alternative medicine , demography , pathology , quantum mechanics , sociology , electron
Herein, we report the isolation and a reactivity study of the first example of an elusive palladium(II) terminal imido complex. This scaffold is an alleged key intermediate for various catalytic processes, including the amination of C−H bonds. We demonstrate facile nitrene transfer with H−H, C−H, N−H, and O−H bonds and elucidate its role in catalysis. The high reactivity is due to the population of the antibonding highest occupied molecular orbital (HOMO), which results in unique charge separation within the closed‐shell imido functionality. Hence, N atom transfer is not necessarily associated with the high valency of the metal (Pd III , Pd IV ) or the open‐shell character of a nitrene as commonly inferred.