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- Title
CNH<sub>2</sub> Bond Formation Mediated by Iridium Complexes.
- Authors
Mena, Inmaculada; Casado, Miguel A.; Polo, Víctor; García-Orduña, Pilar; Lahoz, Fernando J.; Oro, Luis A.
- Abstract
In the presence of phosphanes (PR3), the amido-bridged trinuclear complex [{Ir(μ-NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η2-4-κ-C12H8F4N)(PR3)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)(PMePh2)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 NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule.
- Subjects
BOND formation mechanism; IRIDIUM compounds; COMPLEX compounds; PHOSPHINES; COUPLING agents (Chemistry); DIOLEFINS
- Publication
Angewandte Chemie, 2014, Vol 126, Issue 36, p9781
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201405237