Unusual formation and reactivity of a diplatinum μ-phenylethenylidene complex: Synthesis and structures of cis,cis-[(PPh)(CF) Pt(μ-η:η-CHPhCCO)Pt(PPh )] and cis,cis-[(PPh)Pt{μ-η(C,S):η
Organometallics, ISSN: 0276-7333, Vol: 15, Issue: 3, Page: 1014-1022
1996
- 35Citations
- 4Captures
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Article Description
The μ-phenylethenylidene-bridged diplatinum complex [(OC)(CF)Pt(μ-C=CHPh)Pt-(PPh )], 1, synthesized from the reaction between the mononuclear alkynyl-hydride trans-[Pt(C≡CPh)H(PPh)] and cis-[Pt(CF)(CO)(THF)] (THF = tetrahydrofuran), displays a remarkable reactivity associated with the μ-vinylidene ligand under mild conditions. The reaction of 1 with PPh (molar ratio 1:1) produces an unprecedented reductive coupling of the CO ligand and the vinylidene bridging group to give the compound cis,cis-[(PPh)(CF) -Pt(μ-η:η-CHPhCCO)Pt(PPh )], 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-[(PPh)Pt{μ-η(C,S):η (C)-C(SPh)(CHPh)}Pt(CF) (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.
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