| Abstract
| - The vinylruthenium(II) compounds [Ru(CHCH2)(CH3CN)2(PCy3)2]X [X = PF6- (2a), BPh4- (2b), B(Arf)4- (2c), BF4- (2d)] were prepared either from the hydrido(vinylidene) precursor [RuHCl(CCH2)(PCy3)2] (1a) on treatment with MX in acetonitrile or by salt metathesis from 2a; the molecular structure of 2b was determined crystallographically. Protonation of 2c or 2d with, respectively, [H(OEt2)2]B(Arf)4 or HBF4 gave [Ru(CHCH3)(CH3CN)2(PCy3)2]X2 (4a,b), which represent the first dicationic five-coordinate carbeneruthenium(II) complexes.
- The reaction of the vinylidene(hydrido)ruthenium(II) compound [RuHCl(CCH2)(PCy3)2] (1a) withexcess KPF6 in CH2Cl2/CH3CN affords the five-coordinate vinyl complex [Ru(CHCH2)(CH3CN)2(PCy3)2]PF6(2a), which on treatment with NaBPh4 or NaB(Arf)4gives the tetraaryloborate salts 2b and 2c in excellentyields. The six-coordinate compounds [Ru(CHCHPh)(CH3CN)3(PiPr3)2]X (3a, X = Cl; 3b, X = PF6) wereobtained in a similar route using [RuHCl(CCHPh)(PiPr3)2] (1b) as the starting material. Protonation of 2cor 2d (X = BF4) with, respectively, [H(OEt2)2]B(Arf)4 orHBF4 yields [Ru(CHCH3)(CH3CN)2(PCy3)2]X2 (4a,b),which to the best of our knowledge represent the firstdicationic carbeneruthenium(II) complexes.
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