As a result of the strong electrophilic character of the Pt bound to O, the phosphinito-bridged Pt1 complex [(PHCy2)R(μ-PCy 2){κ2P, O-μ-P(O)Cy2}Pt(PHCy 2)](Pt-Pt) (1) undergoes attack at the O-bound Pt atom by molecules such as diand tricyclohexylphosphane, dicyclohexylphosphane oxide, and dicyclohexylphosphane sulfide. Thus, reaction of 1 with PHCy2 gives the symmetric PtI dimer [(PHCy2)Pt(μ-PCy 2)]2(Pt-Pt) (2), while the hydrido-bridged complex syn-[(PHCy2){κP-P(O)Cy2}Pt(μ-PCy 2)(μ-H)Pt(PHCy2){κP-P(O)Cy2}](Pt-Pt) (4) is obtained from reaction of 1 with P(O)HCy2; the thiophosphinito complex [(PHCy2)Pt(μ-PCy2){κ2P,S- μ-P(S)Cy2}Pt(PHCy2)](Pt-Pt) (8) forms selectively in reaction of 1 with P(S)HCy2. For comparison, the reaction with PCy3 results only in ligand substitution, affording [(PCy 3)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy 2}Pt(PHCy2)](Pt-Pt) (5). DFT studies confirmed the remarkable electrophilicity of the oxygen-bound Pt and shed light on the nature of the metal-metal bond in Pt dimers.

Reactivity of a Phosphinito-Bridged Pt(I)-Pt(I) Complex with Nucleophiles: Substitution versus Addition / Gallo, Vito; Latronico, Mario; Mastrorilli, Pietro; Nobile, Cf; Polini, F; Re, N; Englert, U.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 47:11(2008), pp. 4785-4795. [10.1021/ic800045u]

Reactivity of a Phosphinito-Bridged Pt(I)-Pt(I) Complex with Nucleophiles: Substitution versus Addition

GALLO, Vito;LATRONICO, Mario;MASTRORILLI, Pietro;
2008-01-01

Abstract

As a result of the strong electrophilic character of the Pt bound to O, the phosphinito-bridged Pt1 complex [(PHCy2)R(μ-PCy 2){κ2P, O-μ-P(O)Cy2}Pt(PHCy 2)](Pt-Pt) (1) undergoes attack at the O-bound Pt atom by molecules such as diand tricyclohexylphosphane, dicyclohexylphosphane oxide, and dicyclohexylphosphane sulfide. Thus, reaction of 1 with PHCy2 gives the symmetric PtI dimer [(PHCy2)Pt(μ-PCy 2)]2(Pt-Pt) (2), while the hydrido-bridged complex syn-[(PHCy2){κP-P(O)Cy2}Pt(μ-PCy 2)(μ-H)Pt(PHCy2){κP-P(O)Cy2}](Pt-Pt) (4) is obtained from reaction of 1 with P(O)HCy2; the thiophosphinito complex [(PHCy2)Pt(μ-PCy2){κ2P,S- μ-P(S)Cy2}Pt(PHCy2)](Pt-Pt) (8) forms selectively in reaction of 1 with P(S)HCy2. For comparison, the reaction with PCy3 results only in ligand substitution, affording [(PCy 3)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy 2}Pt(PHCy2)](Pt-Pt) (5). DFT studies confirmed the remarkable electrophilicity of the oxygen-bound Pt and shed light on the nature of the metal-metal bond in Pt dimers.
2008
Reactivity of a Phosphinito-Bridged Pt(I)-Pt(I) Complex with Nucleophiles: Substitution versus Addition / Gallo, Vito; Latronico, Mario; Mastrorilli, Pietro; Nobile, Cf; Polini, F; Re, N; Englert, U.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 47:11(2008), pp. 4785-4795. [10.1021/ic800045u]
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11589/2075
Citazioni
  • Scopus 25
  • ???jsp.display-item.citation.isi??? 23
social impact