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Inmaculada Mena Miguel A. Casado Víctor Polo Pilar García‐Ordua Fernando J. Lahoz Luis A. Oro 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(36):9781-9785
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 C N 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. 相似文献
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