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Ruthenium acetate complexes as versatile probes of metal-ligand interactions: Insight into the ligand effects of vinylidene, carbene, carbonyl, nitrosyl and isocyanide

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Publication details

DatePublished - 1 Mar 2012
Issue number9
Pages (from-to)1493-1506
Original languageEnglish


Reaction of cis-Ru( -OAc) (PPh ) with two-electron donor ligands L results in the formation of complexes trans-[Ru( -OAc)( -OAc)L(PPh ) ] (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 R {OH}) may be prepared from related reactions with propargyl alcohols HC=CCR R {OH}. Treatment of cis-Ru(κ - OAc) (PPh ) with ω-alkynols HC=C(CH ) OH (n = 2-4) results in the formation of oxacyclocarbene complexes [L = CCH (CH ) O]. 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( -OAc) (PPh ) ] acts as a precursor for the formation of the complexes trans-[Ru( -OAc)( -OAc)L(PPh ) ] 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.

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