Acetato and acetylacetonato ruthenium(II) complexes containing SbPri,3, PPri,3 and PCy3 as ligands

The triply bridged binuclear ruthenium complex [{Ru(eta(1)-O2CMe)(SbPr3i)(2)}(2)(mu-O2CMe)(2)(mu-OH2)] 2 was prepared from [Ru(eta(3)-C5H2)(2)(SbPr3i)(2)] 1 and MeCO2H in the presence of water. Its molecular structure was determined by X-ray crystallography. The bis(acetylacetonato) complex [Ru(acac)(2)(SbPr3i)(2)] 3, obtained either from 1 or from [Ru(acac)(3)], is a suitable starting material for the preparation of monosubstituted derivatives [Ru(acac)(2)(SbPr3i)L] (L = PCy3 4, PPr3i, 5, C2H4 7 or C=CHPh 8) as well as of [Ru(acac)(2)(PPr3i)(2)] 6. Ligand-displacement reactions of 6 with PhC=CR (R = H or SiMe3) and HC=CCPh2(O2CMe) led to the vinylidene-and allenylidene-ruthenium complexes [Ru(acac)(2)(PPr31)L] [L = C=CHPh 9, C=C(SiMe3)Ph 10 or C=C=CPh2 11], respectively. Treatment of 2 with PCy3 and PPr3i gave the compounds [Ru(O2CMe)(2)(PR3)(2)] (R = Cy or PPr3i), of which the first smoothly reacted with HC=CR to yield [Ru(eta(2)-O2CMe)(eta(1)-O2CMe)(=C=CHR)(PCy3)(2)] (R = Ph or CO2Me).