Mono- and bis-η1-ketenyl Pt(II) complexes have been synthesized by reacting Zeise's salt or the related dimeric compound, [{PtCl2(C2H4)}2], with the oxocumulenic ylide ketenylidenetriphenylphosphorane, Ph3PCCO, 1, in suitable ratios. In particular, the η1-ketenyl derivative, trans-[PtCl2(C2H4){η1-C(PPh3)CO}], 2, has been isolated and characterized. The reaction of 2 with one more equivalent of 1 displaces the coordinated ethylene giving the first stable bis-η1-ketenyl derivative, trans-[PtCl2{η1-C(PPh3)CO}2], 6. The X-ray crystal structure of 6 shows a trans centrosymmetric geometry around Pt, with the PCCO moiety and the metal lying in a plane that forms an angle of 65° with the Pt(II) coordination plane. Density functional calculations indicate that steric effects play a leading role in determining such an arrangement. Data on the reactivity of 2 and 6 are also reported.
Organometallic Chemistry of Ph3PCCO. Synthesis, Characterization, X-ray Structure Determination, and Density Functional Study of the First Stable Bis-η1-ketenyl Complex, trans-[PtCl2{η1-C(PPh3)CO}2]
BERTANI, ROBERTA;CASARIN, MAURIZIO;MACCATO, CHIARA;PANDOLFO, LUCIANO;
2000
Abstract
Mono- and bis-η1-ketenyl Pt(II) complexes have been synthesized by reacting Zeise's salt or the related dimeric compound, [{PtCl2(C2H4)}2], with the oxocumulenic ylide ketenylidenetriphenylphosphorane, Ph3PCCO, 1, in suitable ratios. In particular, the η1-ketenyl derivative, trans-[PtCl2(C2H4){η1-C(PPh3)CO}], 2, has been isolated and characterized. The reaction of 2 with one more equivalent of 1 displaces the coordinated ethylene giving the first stable bis-η1-ketenyl derivative, trans-[PtCl2{η1-C(PPh3)CO}2], 6. The X-ray crystal structure of 6 shows a trans centrosymmetric geometry around Pt, with the PCCO moiety and the metal lying in a plane that forms an angle of 65° with the Pt(II) coordination plane. Density functional calculations indicate that steric effects play a leading role in determining such an arrangement. Data on the reactivity of 2 and 6 are also reported.Pubblicazioni consigliate
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