Acetato and acetylacetonato ruthenium(II) complexes containing SbPri3, PPri3 and PCy3 as ligands‡

Abstract

The triply bridged binuclear ruthenium complex [{Ru(η¹-O₂CMe)(SbPrⁱ₃)₂}₂(µ-O₂CMe)₂(µ-OH₂)] 2 was prepared from [Ru(η³-C₃H₅)₂(SbPrⁱ₃)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(SbPrⁱ₃)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(SbPrⁱ₃)L] (L = PCy₃ 4, PPrⁱ₃ 5, C₂H₄ 7 or CCHPh 8) as well as of [Ru(acac)₂(PPrⁱ₃)₂] 6. Ligand-displacement reactions of 6 with PhCCR (R = H or SiMe₃) and HCCCPh₂(O₂CMe) led to the vinylidene- and allenylidene-ruthenium complexes [Ru(acac)₂(PPrⁱ₃)L] [L = CCHPh 9, CC(SiMe₃)Ph 10 or CCCPh₂ 11], respectively. Treatment of 2 with PCy₃ and PPrⁱ₃ gave the compounds [Ru(O₂CMe)₂(PR₃)₂] (R = Cy or PPrⁱ₃), of which the first smoothly reacted with HCCR to yield [Ru(η²-O₂CMe)(η¹-O₂CMe)(CCHR)(PCy₃)₂] (R = Ph or CO₂Me).