Organometallic Chemistry of Ph3PC=C=O. Synthesis, Characterization, X-ray Structure Determination, and Density Functional Study of the First Stable Bis-
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- 作者：Roberta Bertani ; Maurizio Casarin ; Paolo Ganis ; Chiara Maccato ; Luciano Pandolfo ; Alfonso Venzo ; Andrea Vittadini ; and Livio Zanotto
- 刊名：Organometallics
- 出版年：2000
- 出版时间：April 3, 2000
- 年：2000
- 卷：19
- 期：7
- 页码：1373 - 1383
- 全文大小：267K
- 年卷期：v.19,no.7(April 3, 2000)
- ISSN：1520-6041
文摘
Mono- and bis-
1-ketenyl Pt(II) complexes have been synthesized by reacting Zeise's saltor the related dimeric compound, [{PtCl2(C2H4)}2], with the oxocumulenic ylide ketenylidenetriphenylphosphorane, Ph3PC=C=O, 1, in suitable ratios. In particular, the 1-ketenylderivative, trans-[PtCl2(C2H4){1-C(PPh3)CO}], 2, has been isolated and characterized. Thereaction of 2 with one more equivalent of 1 displaces the coordinated ethylene giving thefirst stable bis-1-ketenyl derivative, trans-[PtCl2{1-C(PPh3)CO}2], 6. The X-ray crystalstructure of 6 shows a trans centrosymmetric geometry around Pt, with the PCCO moietyand the metal lying in a plane that forms an angle of ~65
with the Pt(II) coordinationplane. Density functional calculations indicate that steric effects play a leading role indetermining such an arrangement. Data on the reactivity of 2 and 6 are also reported.
1-ketenyl Pt(II) complexes have been synthesized by reacting Zeise's saltor the related dimeric compound, [{PtCl2(C2H4)}2], with the oxocumulenic ylide ketenylidenetriphenylphosphorane, Ph3PC=C=O, 1, in suitable ratios. In particular, the 1-ketenylderivative, trans-[PtCl2(C2H4){1-C(PPh3)CO}], 2, has been isolated and characterized. Thereaction of 2 with one more equivalent of 1 displaces the coordinated ethylene giving thefirst stable bis-1-ketenyl derivative, trans-[PtCl2{1-C(PPh3)CO}2], 6. The X-ray crystalstructure of 6 shows a trans centrosymmetric geometry around Pt, with the PCCO moietyand the metal lying in a plane that forms an angle of ~65 with the Pt(II) coordinationplane. Density functional calculations indicate that steric effects play a leading role indetermining such an arrangement. Data on the reactivity of 2 and 6 are also reported.