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CNH 2 Bond Formation Mediated by Iridium Complexes
Author(s) -
Mena Inmaculada,
Casado Miguel A.,
Polo Víctor,
GarcíaOrduña Pilar,
Lahoz Fernando J.,
Oro Luis A.
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.201405237
Subject(s) - moiety , iridium , chemistry , nucleophile , molecule , stereochemistry , ammonia , medicinal chemistry , organic chemistry , catalysis
Abstract In the presence of phosphanes (PR 3 ), the amido‐bridged trinuclear complex [{Ir(μ‐NH 2 )(tfbb)} 3 ] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2‐η 2 ‐4‐κ‐C 12 H 8 F 4 N)(PR 3 ) 3 ], which are the products of the CN coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e − complex [Ir(Cl)(tfbb)(PMePh 2 ) 2 ] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH 2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule.