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.

Pt−Mo and Pt−W Mixed-Metal Clusters with Chelating or Bridging Diphosphine Short-Bite Ligands (Ph2P)2NH and (Ph2P)2N(CH2)9CH3: A Combined Synthetic and Theoretical Study / Stefano, Todisco; Gallo, Vito; Mastrorilli, Pietro; Latronico, Mario; Nazzareno, Re; Francesco, Creati; Pierre, Braunstein. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 51:21(2012), pp. 11549-11561. [10.1021/ic301445h]

Pt−Mo and Pt−W Mixed-Metal Clusters with Chelating or Bridging Diphosphine Short-Bite Ligands (Ph2P)2NH and (Ph2P)2N(CH2)9CH3: A Combined Synthetic and Theoretical Study

GALLO, Vito;MASTRORILLI, Pietro;LATRONICO, Mario;
2012-01-01

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.
2012
Pt−Mo and Pt−W Mixed-Metal Clusters with Chelating or Bridging Diphosphine Short-Bite Ligands (Ph2P)2NH and (Ph2P)2N(CH2)9CH3: A Combined Synthetic and Theoretical Study / Stefano, Todisco; Gallo, Vito; Mastrorilli, Pietro; Latronico, Mario; Nazzareno, Re; Francesco, Creati; Pierre, Braunstein. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 51:21(2012), pp. 11549-11561. [10.1021/ic301445h]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11589/1530
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