Preparation of trifluorophosphaneruthenium(II) complexes from #eta#~3:#eta#~3-cyclooctadienediylruthenium(IV) compounds as precursors

摘要

The dinuclear cyclooctadienediylruthenium(IV) compound [{RuCl_2(#eta#~3:#eta#~3-C_(10)H_(16)}_2] (1) reacts with PCy_3 in 2-propanol under an H_2 atmosphere to give the hydrido(dihydrogen) complex [RuHCl(H_2)(PCy_3)_2] (2) in nearly quantitative yield. Treatment of 1 with PCy_3, PiPr_3Ph under argon affords the mononuclear products [RuCl_2(#eta#~3:#eta#~3-C_(10)H_(16))(PR_3)] (3-5) by chloride-bridge cleavage. The corresponding compound 6 with PF_3 as phosphane ligand reacts with PCy_3 by nucleophilic attack of PCy_3 at the carbon atom C3 of the dienediyl chain to give the zwitterionic #eta#~2:#eta#~3-alkene(allyl)ruthenium(II) complex [RuCl_2{#eta#~2:#eta#~3-CH_2=C(Me)-CH(PCy_3)(CH_2)CHC(Me)CH_2}(PF_3)] (7) the crystal and molecular structures of which have been determined. The reaction of 7 with excess PCy_3 in the presence of H_2 affords the fivecoordinate hydrido compound [RuHCl(PF_3)(PCy_3)_2] (8), which upon teatment with acetylene gives the vinyl derivative [RuCl(CH=CH_2)(PF_3)(PCy_3)_2] (9). The related cationic carbene complex [RuCl(=CHCH_3)(PF_3)(PCy_3)_2]BF_4 (10) is obtained by protonation of 9 with HBF_4 in ether.