Abstract
The complex [Ru{HB(pz) 3 }(cod)Cl] 1 (cod = cycloocta-1,5-diene) reacted with P(C 6 H 11 ) 3 (1 equivalent) in boiling dimethylformamide (dmf) to give the highly air-sensitive intermediate [Ru{HB(pz) 3 }{P(C 6 H 11 ) 3 }Cl(dmf)] which, on exposure to air in either ethanol or methanol as the solvent, was converted to the ruthenium(III) complexes [Ru{HB(pz) 3 }{P(C 6 H 11 ) 3 }Cl(OCH 2 R)] (R = Me 2a or H 2b) in good yields. Complex 2b has been characterized by X-ray crystallography. Treatment of 2a or 2b with L = MeCN, pyridine, CO, P(OMe) 3 , or PMe 3 in CH 2 Cl 2 afforded the (diamagnetic) ruthenium(II) compounds [Ru{HB(pz) 3 }{P(C 6 H 11 ) 3 }(Cl)L] 3–7. Most remarkably, 2a or 2b reacted also with terminal alkynes HCCR (R = Ph, CO 2 Et, Bu n or SiMe 3 ) giving the neutral vinylidene complexes [Ru{HB(pz) 3 }{P(C 6 H 11 ) 3 }Cl (CCHR)] 8–11. Preliminary results of a study of the catalytic activity of 2 are also presented. Thus, 2a and 2b catalysed the dimerization of some terminal alkynes HCCR (R = Ph, CO 2 Et or SiMe 3 ).
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