The Pt-2((II)) isomeric terminal hydrides [(CO)(H)Pt(mu-PBu21)(2)Pt((PBu2H)-H-1)]CF ISO, (1a), and [(CO)Ptmu-Bu-2(1))(2)Pt((PBu2H)-H-1)(H)]CF3SO3 (1b), react rapidly with 1 atm of carbon monoxide to give the same mixture of two isomers of the P-2((I)) dicarbonyl [Pt-2(mu-PBu21)(CO)(2)((PBu2H)-H-1)(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 la and 1b towards carbon disulfide or isoprene. In both cases 1b reacts slowly to afford [Pt-2(mu-PBu21)(mu,eta(2),eta(2)-CS2)((PBu2H)-H-1)(2)]CF3SO3 (4-Pt), and [Pt-2(mu-PBu21)(mu,eta(2),eta(2)-isoprene) ((PBu2H)-H-1)(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. (

Ligand induced P-H bond formation and a comparison of the reactivity of two isomers of the carbonyl hydride [Pt-2( mu-PBu2t)(2)(H)(CO)((PBu2H)-H-t)]CF3SO3 / V. Cittadini, P. Leoni, L. Marchetti, M. Pasquali, A. Albinati. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - 330:1(2002), pp. 25-32.

Ligand induced P-H bond formation and a comparison of the reactivity of two isomers of the carbonyl hydride [Pt-2( mu-PBu2t)(2)(H)(CO)((PBu2H)-H-t)]CF3SO3

A. Albinati
Ultimo
2002

Abstract

The Pt-2((II)) isomeric terminal hydrides [(CO)(H)Pt(mu-PBu21)(2)Pt((PBu2H)-H-1)]CF ISO, (1a), and [(CO)Ptmu-Bu-2(1))(2)Pt((PBu2H)-H-1)(H)]CF3SO3 (1b), react rapidly with 1 atm of carbon monoxide to give the same mixture of two isomers of the P-2((I)) dicarbonyl [Pt-2(mu-PBu21)(CO)(2)((PBu2H)-H-1)(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 la and 1b towards carbon disulfide or isoprene. In both cases 1b reacts slowly to afford [Pt-2(mu-PBu21)(mu,eta(2),eta(2)-CS2)((PBu2H)-H-1)(2)]CF3SO3 (4-Pt), and [Pt-2(mu-PBu21)(mu,eta(2),eta(2)-isoprene) ((PBu2H)-H-1)(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. (
hydride chemistry, Platinum chemistry, phosphido ligands; platinum; dinuclear complexes; phosphide complexes; secondary phosphine; proton transfer
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/252918
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