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)]
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
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.