Abstract
Reactions between RUCI(PPh3)2(η-C5H5),
RuCI(L2)(η-C5H5)(L2
= dppm or dppe) or OsBr(PPh3)2-(η-C5H5)
and the alk-1-ynes HC2R (R = Me, Pr, CO2Me, Ph, C6H4F-p or C6F5), in the
presence of NH4PF6, NH4BF4 or NaBPh4,
have given the corresponding cationic η1-vinylidene
complexes [Ru(C=CHR)(PPh3)2(η-C5H5)]+,[Ru(C=CHPh)(L2)(η-C5H5)]+
or [Os(C=CHP~)(PPh3)2(η-C5H5)]+.
These cations are readily deprotonated to give the corresponding η1-ethynyl derivatives
Ru(C2R)-(PPh3)2(η-C5H5),
Ru(C2Ph)(L2)(η-C5H5) or OS(C2Ph)(PPh3)2(η-C5H5).
Addition of HPF6 or [R'3O]PF6 (R' = Me or Et)
to the latter affords the vinylidene complexes containing C=CHR and C=CRR'
ligands (R = Me, Pr, CO2Me, Ph, C6H4F-p or C6F5; R' = Me
or Et), respectively. The vinylidene complexes are characterized by ν(CC) bands at c. 1650 cm-1 and the metal-bonded carbon (13C)
resonance at c. 360 ppm.
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