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Cyclopentadienyl-ruthenium and-Osmium Chemistry. IX. Some Substituted η1-Vinylidene and η1-Acetylide Complexes
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Reactions between RUCI(PPh3)2( ? -C5H5), RuCI(L2)( ? -C5H5)(L2 = dppm or dppe) or OsBr(PPh3)2-( ? -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 ? 1-vinylidene complexes [Ru(C=CHR)(PPh3)2(?-C5H5)]+,[Ru(C=CHPh)(L2)(?-C5H5)]+ or [Os(C=CHP~)(PPh3)2(?-C5H5)]+. These cations are readily deprotonated to give the corresponding ? 1-ethynyl derivatives Ru(C2R)-(PPh3)2(?-C5H5), Ru(C2Ph)(L2)(?-C5H5) or OS(C2Ph)(PPh3)2(?-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 ? (CC) bands at c . 1650 cm-1 and the metal-bonded carbon (13C) resonance at c . 360 ppm.
Title: Cyclopentadienyl-ruthenium and-Osmium Chemistry. IX. Some Substituted η1-Vinylidene and η1-Acetylide Complexes
Description:
Reactions between RUCI(PPh3)2( ? -C5H5), RuCI(L2)( ? -C5H5)(L2 = dppm or dppe) or OsBr(PPh3)2-( ? -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 ? 1-vinylidene complexes [Ru(C=CHR)(PPh3)2(?-C5H5)]+,[Ru(C=CHPh)(L2)(?-C5H5)]+ or [Os(C=CHP~)(PPh3)2(?-C5H5)]+.
These cations are readily deprotonated to give the corresponding ? 1-ethynyl derivatives Ru(C2R)-(PPh3)2(?-C5H5), Ru(C2Ph)(L2)(?-C5H5) or OS(C2Ph)(PPh3)2(?-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 ? (CC) bands at c .
1650 cm-1 and the metal-bonded carbon (13C) resonance at c .
360 ppm.
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