Journal of Organometallic Chemistry p. 127 - 141 (1997)
Update date:2022-08-05
Topics:
Werner
Braun
Daniel
Gevert
Schulz
Monomeric carboxylatoruthenium(II) complexes [C5R5Ru(η2-O2CR′)(PPh3)] (R = H, Me, R′ = Me, tBu, CF3) were prepared by ligand displacement from [(C5R5)Ru(η3-2-MeC3H4)(PPh3)] and R′CO2H. From a similar route, the tosylato and pentachlorphenolato derivatives [C5H5Ru{O2SO(p-C6H4Me)}(PPh3)]n and [C5H5Ru(η2-OC6Cl5)(PPh3)] were obtained. On treatment with PhNH2, CO, PPh3 and O2, they reacted to give the complexes [C5H5Ru{O2SO(p-C6H4Me)}(L)(PPh3)] and [C5H5Ru(OC6Cl5)(CO)(PPh3)] respectively. The reaction of [C5R5Ru(η2-O2CR′)(PPh3)] (R′ = Me, tBu) with terminal alkynes HC≡CR (R = CO2Me, Ph) yielded the vinylesterruthenium(II) compounds [C5H5Ru{κ2(C,O)-C(=CHR)OC(R′)=O}(PPh3)] for which a resonance structure involving a carboxylato(vinylidene) species is postulated. The carbene half-sandwich type complexes [C5H5RuCl(=CRR′)(PPh3)] (R and R′ = C6H4X) were prepared in two steps from [C5H5Ru(η2-O2CMe)(PPh3)], N2CRR′ and either Al2O3/Cl- or Et3NHCl. The molecular structure of [C5Me5Ru(η2-O2CtBu)(PPh3)] and [C5H5RuCl(=CPh2)(PPh3)] have been determined by X-ray single-crystal structural investigations.
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(1997)
