title: Reactivity of a phosphinito-bridged PtI-PtI complex with nucleophiles: substitution versus addition.
abstract: As a result of the strong electrophilic character of the Pt bound to O, the phosphinito-bridged PtI complex [(PHCy2)Pt(micro-PCy2){kappa2P,O-micro-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) undergoes attack at the O-bound Pt atom by molecules such as di- and tricyclohexylphosphane, dicyclohexylphosphane oxide, and dicyclohexylphosphane sulfide. Thus, reaction of 1 with PHCy2 gives the symmetric PtI dimer [(PHCy2)Pt(micro-PCy2)]2(Pt-Pt) (2), while the hydrido-bridged complex syn-[(PHCy2){kappaP-P(O)Cy2}Pt(micro-PCy2)(micro-H)Pt(PHCy2){kappaP-P(O)Cy2}](Pt-Pt) (4) is obtained from reaction of 1 with P(O)HCy2; the thiophosphinito complex [(PHCy2)Pt(micro-PCy2){kappa2P,S-micro-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 [(PCy3)Pt(micro-PCy2){kappa2P,O-micro-P(O)Cy2}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.
authors.affiliation: Dipartimento di Ingegneria delle Acque e di Chimica del Politecnico di Bari, via Orabona 4, I-70125 Bari, Italy.
authors.forename: Vito
authors.initials: V
authors.lastname: Gallo
authors.forename: Mario
authors.initials: M
authors.lastname: Latronico
authors.forename: Piero
authors.initials: P
authors.lastname: Mastrorilli
authors.forename: Cosimo F
authors.initials: CF
authors.lastname: Nobile
authors.forename: Flavia
authors.initials: F
authors.lastname: Polini
authors.forename: Nazzareno
authors.initials: N
authors.lastname: Re
authors.forename: Ulli
authors.initials: U
authors.lastname: Englert
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D017671:Platinum Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D017671:Platinum Compounds