摘要 : Reaction of cis-Ru(~2-OAc) _2(PPh _3) _2 with two-electron donor ligands L results in the formation of complexes trans-[Ru(~1-OAc)(~2-OAc)L(PPh _3) _2] (L = CO, NO ~+, CNtBu). Vinylidene complexes (L = C=CHR) may be prepared from ... 展开 Reaction of cis-Ru(~2-OAc) _2(PPh _3) _2 with two-electron donor ligands L results in the formation of complexes trans-[Ru(~1-OAc)(~2-OAc)L(PPh _3) _2] (L = CO, NO ~+, CNtBu). Vinylidene complexes (L = C=CHR) may be prepared from the corresponding reaction with terminal alkynes HC=CR, and species containing hydroxyvinylidene ligands (L = C=CHCR ~1R ~2{OH}) may be prepared from related reactions with propargyl alcohols HC=CCR ~1R ~2{OH}. Treatment of cis-Ru(κ ~2- OAc) _2(PPh _3) _2 with ω-alkynols HC=C(CH _2) _nOH (n = 2-4) results in the formation of oxacyclocarbene complexes [L = CCH _2(CH _2) _nO]. An analysis of the spectroscopic data and the structural metrics (as determined by X-ray crystallography) of this series of complexes allows for the relative donor/acceptor properties of the ligand L to be evaluated. This comparison indicates that the vinylidene ligand behaves in a similar fashion to the isocyanide ligand. The complex cis-[Ru(~2-OAc) _2(PPh _3) _2] acts as a precursor for the formation of the complexes trans-[Ru(~1-OAc)(~2-OAc)L(PPh _3) _2] where L is a two-electron donor, σ-donor/π-acceptor ligand. The structural and spectroscopic data of these species provide insight into the relative electron demand of the ligands L. 收起