Abstract

The reactivity of the complexes [PtCl2{Ph2PN(R)PPh2-P,P}] (R = −H, 3; R = −(CH2)9CH3, 8) toward group 6 carbonylmetalates Na[MCp(CO)3] (M = W or Mo, Cp = cyclopentadienyl) was explored. When R = H, the triangular clusters [PtM2Cp2(CO)5(μ-dppa)] (M = W, 4; M = Mo, 5), in which the diphosphane ligand bridges a Pt-M bond, were obtained as the only products. When R = −(CH2)9CH3, isomeric mixtures of the triangular clusters [PtM2Cp2(CO)5{Ph2PN(R)PPh2-P,P}], in which the diphosphane ligand chelates the Pt center (M = W, 11; M = Mo, 13) or bridges a Pt–M bond (M = W, 12; M = Mo, 14), were obtained. Irrespective of the M/Pt ratio used when R = −(CH2)9CH3, the reaction of [PtCl2{Ph2PN(R)PPh2-P,P}] with Na[MCp(CO)3] in acetonitrile stopped at the monosubstitution stage with the formation of [PtCl{MCp(CO)3}{Ph2PN(R)PPh2-P,P}] (R = −(CH2)9CH3, M = W, 9; M = Mo, 10), which are the precursors to the trinuclear clusters formed in THF when excess carbonylmetalate was used. The dynamic behavior of the dppa derivatives 4 and 5 in solution as well as that of their carbonylation products 6 and 7, respectively, is discussed. Density functional calculations were performed to study the thermodynamics of formation of 4 and 5 and 11–14, to evaluate the relative stabilities of the chelated and bridged forms and to trace a possible pathway for the formation of the trinuclear clusters.

Autore Pugliese

• Gallo Vito , Latronico Mario , Mastrorilli Pietro

Tutti gli autori

• Stefano Todisco , Gallo V , Pietro Mastrorilli , Mario Latronico , Nazzareno Re , Francesco Creati , Pierre Braunstein

Titolo volume/Rivista

INORGANIC CHEMISTRY

Anno di pubblicazione

2012

ISSN

0020-1669

ISBN

Non Disponibile

Numero di citazioni Wos

Nessuna citazione

Ultimo Aggiornamento Citazioni

Non Disponibile

Numero di citazioni Scopus

7

Ultimo Aggiornamento Citazioni

2017-04-23 03:20:56

Settori ERC

Non Disponibile

Codici ASJC

Non Disponibile