Synthesis and characterization of trimetallic ruthenium and bimetallic osmium complexes with metal-vinyl linkages

Treatment of RuHCl(CO)(PPh3)3 with 1,3,5-triethynylbenzene produces the trimetallic complex 1,3,5-[Cl(CO)(PPh3)2RuCHCH]3C6H3, which reacts with PMe3 to give 1,3,5-[Cl(CO)(PMe3)3RuCHCH]3C6H3. 1,3,5-[Cl(CO)(PPh3)2RuCHCH]3C6H3 also reacts with pyridine (Py) and 4-phenylpyridine (PhPy) to give 1,3,5-[Cl(CO)(L)(PPh3)2RuCHCH]3C6H3 (L = Py, PhPy). Reactions of OsHCl(CO)(PPh3)3 with ArC⋮CH (Ar = Ph, p-tolyl) produce the six-coordinated insertion products OsCl(CHCHAr)(CO)(PPh3)3. Reaction of OsHCl(CO)(PPh3)3 with 1,3,5-triethynylbenzene produces the bimetallic complex 1-HC⋮C-3,5-[Cl(CO)(PPh3)3OsCHCH]2C6H3, which reacts with PMe3 to give 1-HC⋮C-3,5-[OsCl(CO)(PPh3)2(PMe3)OsCHCH]2C6H3. The electrochemical and second-order NLO properties of some of the new complexes have been investigated.