405877-54-5Relevant academic research and scientific papers
A Series of Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes with [Ru(PCy3)2] and [Ru(PiPr3)2] as Molecular Building Blocks
Jung, Stefan,Ilg, Kerstin,Brandt, Carsten D.,Wolf, Justin,Werner, Helmut
, p. 469 - 480 (2004)
The hydrido(vinylidene) complexes [RuHCl(=C=CHR)(L)2] (R=H, tBu, Ph; L=PCy3, PiPr3) undergo metathesis reactions in the presence of KX (X=I, NCO, OPh, CH3CO2, CF3CO2) to give the substitution products [RuHX(=C=CHR)(L)2] (6-15) in good to excellent yields. Treatment of [RuHX(=C=CHR)(L)2] with HBF4 in diethyl ether affords the cationic carbyneruthenium(II) derivatives [RuHX(-=CCH2R)(OEt2)(L)2]BF4 (17, 18, 20, 21) and [RuH(κ2-O2CCH3)(-=CCH2R)(L)2]BF4 (19, 22). The reactions of [RuHCl(=C=CHR)(L)2] with MX [X= BF4, PF6, BPh4, B(Arf)4] in acetonitrile lead to the formation of cationic five- and six-coordinate vinylruthenium(II) compounds 26a-d and 27a-d of which [Ru(CH=CH2)(CH3CN)2(PCy3)2]BPh4 (26c) has been characterized by X-ray crystallography. The starting material [RuHCl(=C=CHPh)(PiPr3)2]2 reacts with CO to give [RuCl(CH=CHPh)(CO)2(PiPr3)2] (28) and with N2 to produce [RuCl(CH=CHPh)(N2)(PiPr3)2] (29). The molecular structure of 29 has been determined. Protonation of [Ru(CH=CH2)(CH3CN)2(PCy3)2]X and [Ru(CH=CHPh)(CH3CN)3(PiPr3)2]X with HBF4 and HB(Arf)4 yields the dicationic carbene-ruthenium(II) complexes [Ru(=CHCH3)(CH3CN)2(PCy3)2]X2 (30a,b) and [Ru(=CHCH2Ph)(CH3CN)3(PiPr3)2][B(Arf)4]2 (31), the latter of which eliminates styrene to give [Ru(CH3CN)3(PiPr3)2][B(Arf)4]2 (32).
