Ligand induced P---H bond formation and a comparison of the reactivity of two isomers of the carbonyl hydride [Pt2(μ-PBu2)2(H)(CO)(PBu2H)]CF3SO3 |
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Authors: | Valerio Cittadini Piero Leoni Lorella Marchetti Marco Pasquali Alberto Albinati |
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Institution: | a Dipartimento di Chimica e Chimica Industriale, Universita di Pisa, Via Risorgimento 35, I-56126, Pisa, Italy b Istituto di Chimica Farmaceutica, Viale Abruzzi 42, I-20131, Milano, Italy |
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Abstract: | The Pt2 (II) isomeric terminal hydrides (CO)(H)Pt(μ-PBut 2)2Pt(PBut 2H)]CF3SO3 (1a), and (CO)Pt(μ-PBut 2)2Pt(PBut 2H)(H)]CF3SO3 (1b), react rapidly with 1 atm of carbon monoxide to give the same mixture of two isomers of the Pt2 (I) dicarbonyl Pt2(μ-PBut 2)(CO)2(PBut 2H)2]CF3SO3 (3-Pt); the solid state structure of the isomer bearing the carbonyl ligands pseudo-trans to the bridging phosphide was solved by X-ray diffraction. A remarkable difference was instead found between the reactivity of 1a and 1b towards carbon disulfide or isoprene. In both cases 1b reacts slowly to afford Pt2(μ-PBut 2)(μ,η2,η2-CS2)(PBut 2H)2]CF3SO3 (4-Pt), and Pt2(μ-PBut 2)(μ,η2,η2-isoprene) (PBut 2H)2]CF3SO3 (6-Pt), respectively. In the same experimental conditions, 1a is totally inert. A common mechanism, proceeding through the preassociation of the incoming ligand followed by the P---H bond formation between one of the bridging P atoms and the hydride ligand, has been suggested for these reactions. |
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Keywords: | Platinum Dinuclear complexes Phosphide complexes Secondary phosphine Proton transfer |
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