Organometallic chemistry of Ph3PC=C=O. Synthesis, characterization, X-ray structure determination, and density functional study of the first stable bis-eta(1)-ketenyl complex, trans-[PtCL2{eta(1)-C(PPh3)CO}(2)]

Citation
R. Bertani et al., Organometallic chemistry of Ph3PC=C=O. Synthesis, characterization, X-ray structure determination, and density functional study of the first stable bis-eta(1)-ketenyl complex, trans-[PtCL2{eta(1)-C(PPh3)CO}(2)], ORGANOMETAL, 19(7), 2000, pp. 1373-1383
Citations number
100
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
02767333 → ACNP
Volume
19
Issue
7
Year of publication
2000
Pages
1373 - 1383
Database
ISI
SICI code
0276-7333(20000403)19:7<1373:OCOPSC>2.0.ZU;2-O
Abstract
Mono- and bis-eta(1)-ketenyl Pt(II) complexes have been synthesized by reac ting Zeise's salt or the related dimeric compound, [{PtCl2(C2H4)}(2)], with the oxocumulenic ylide ketenyliden-etriphenylphosphorane, Ph3PC=C=O, 1, in suitable ratios. In particular, the yl-ketenyl derivative, trans-[PtCl2(C2 H4){eta(1)-C(PPh3)CO}], 2, has been isolated and characterized. The reactio n of 2 with one more equivalent of 1 displaces the coordinated ethylene giv ing the first stable bis-eta(1)-ketenyl derivative, trans-[PtCl2{eta(1)-C(P Ph3)CO}(2)], 6. The X-ray crystal structure of 6 shows a trans centrosymmet ric geometry around Pt, with the PCCO moiety and the metal lying in a plane that forms an angle of similar to 65 degrees 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.