Alkene complexes of ruthenium(0): crystal structures, isomerism and fluxionality
- 1 January 1994
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 1193-1205
- https://doi.org/10.1039/dt9940001193
Abstract
The ligand arrangements in alkene complexes [Ru(CO)2(alkene)LL′][alkene =E- or Z-MeO2CCHCHCO2Me, L = L′= PMe2Ph or AsMe2Ph, or L = PMe2Ph, L′= P(OMe)3; alkene = H2CCH2, H2CCHCO2Me, E-NCCHCHCN, Z-MeO2CCHCClCO2Me, or E- or Z-MeO2CCHCPhCO2Me, L = L′= PMe2Ph] have been determined by IR and NMR spectroscopy and, in two instances, by X-ray crystallography. Three types of arrangement have been identified: their relative stabilities are discussed in terms of steric interactions between the alkene substituents and the ligands L and L′. Variable-temperature NMR studies on [Ru(CO)2(E-MeO2CCHCHCO2Me)(PMe2Ph)2] have revealed that the complex is fluxional but that the fluxional motion is restricted by these same interactions. With Z-MeO2CCHCHCO2Me, complex formation is accompanied by alkene isomerisation: deuterium labelling experiments have thrown light on the mechanism of isomerisation.Keywords
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