Todd Graham - Reactivity of Terminal Electrophilic Phosphinidene Complexes: Synthesis of the First Rhenium Phosphinidene, [Re(CO)5(η1-PNiPr2)][AlCl4], and Novel Reactions with Azobenzene

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      Todd W. Graham, Renan P.-Y. Cariou, Javier Sánchez-Nieves, Anna   E.  Allen, Konstantin A. Udachin, Rachid Regragui, and   Arthur J. Carty


      The first terminal rhenium phosphinidene complex,   [Re(CO)51-PNiPr2)][AlCl4],   has been synthesized by chloride abstraction from   [Re(CO)5{P(Cl)(NiPr2)}].    The electrophilic character of the terminal phosphinidene ligand   is  demonstrated by phosphine addition at the unsaturated   phosphorus center  and by novel reactions with azobenzene,   PhNNPh,  which   generate, via C−H activation and P−N and P−C bond   formation,  coordinated benzodiazaphosphole ligands. The   cations   [Re(CO)5P(PPh3)NiPr2]+  and   [Re(CO)5{P(PhNNHC6H4)NiPr2}]+  have been crystallographically characterized as their   AlCl4- salts. The corresponding late-metal   terminal phosphinidene complexes   [Co(CO)3(PR3)(η1-PNiPr2)][AlCl4]   (R = Ph, Et) also afford coordinated benzodiazaphospholes via   reaction with PhNNPh.

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