ACETATO AND ACETYLACETONATO RUTHENIUM(II) COMPLEXES CONTAINING SBPRI(3), PPRI(3) AND PCY3 AS LIGANDS

The triply bridged binuclear ruthenium complex eta(1)-O2CMe)(SbPr3i)(2 )}(2)(mu-O2CMe)(2)(mu-OH2)] 2 was prepared from [Ru(eta(3)-C5H2)(2)(Sb Pr3i)(2)] 1 and MeCO2H in the presence of water. Its molecular structu re was determined by X-ray crystallography. The bis(acetylacetonato) c omplex [Ru(acac)(2)(SbPr3i)(2)] 3, obtained either from 1 or from [Ru( acac)(3)], is a suitable starting material for the preparation of mono substituted 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-di splacement reactions of 6 with PhC=CR (R = H or SiMe3) and HC=CCPh2(O2 CMe) led to the vinylidene-and allenylidene-ruthenium complexes [Ru(ac ac)(2)(PPr31)L] [L = C=CHPh 9, C=C(SiMe3)Ph 10 or C=C=CPh2 11], respec tively. Treatment of 2 with PCy3 and PPr3i gave the compounds [Ru(O2CM e)(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).