Unusual Formation and Reactivity of a Diplatinum mu-phenylethenylidene Complex: Synthesis and Structures of cis,cis-[(PPh3)(C6F5)2Pt(mu-eta1-eta3-CHPhCCO)Pt(PPh3)2] and cis,cis-[(PPh3)2Pt{mu-eta2(C,S):eta1(CC(SPh)(CH2Ph)}Pt(C6F5)2(CO)] Dinuclear Compounds

  1. Ara, I. 2
  2. Berenguer, J.R. 1
  3. Forniés, J. 2
  4. Lalinde, E. 1
  5. Tomás, M. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

Revista:
Organometallics

ISSN: 0276-7333

Any de publicació: 1996

Volum: 15

Número: 3

Pàgines: 1014-1022

Tipus: Article

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DOI: 10.1021/OM950891X SCOPUS: 2-s2.0-0000886358 WoS: WOS:A1996TU70200019 GOOGLE SCHOLAR

Altres publicacions en: Organometallics

Repositori institucional: lock_openAccés obert Editor

Resum

The μ-phenylethenylidene-bridged diplatinum complex [(OC)(C6F5)2Pt(μ-C=CHPh)Pt-(PPh 3)2], 1, synthesized from the reaction between the mononuclear alkynyl-hydride trans-[Pt(C≡CPh)H(PPh3)2] and cis-[Pt(C6F5)2(CO)(THF)] (THF = tetrahydrofuran), displays a remarkable reactivity associated with the μ-vinylidene ligand under mild conditions. The reaction of 1 with PPh3 (molar ratio 1:1) produces an unprecedented reductive coupling of the CO ligand and the vinylidene bridging group to give the compound cis,cis-[(PPh3)(C6F5) 2-Pt(μ-η1:η3-CHPhCCO)Pt(PPh 3)2], 2, which contains an expanded, unsaturated benzylideneketene bridging ligand. On the other hand, treatment of 1 with PhSH generates the new diplatinum compound cis,cis-[(PPh3)2Pt{μ-η2(C,S):η 1(C)-C(SPh)(CH2Ph)}Pt(C6F5) 2(CO)], 3, formed by a formal addition of the PhSH to the carbon-carbon double bond of the vinylidene group in 1. The structures of 2 and 3 have been fully elucidated by X-ray diffraction studies.