The preparation of mixed ligand ruthenocenes containing bulky cyclopentadienyl ligands. Crystal structures of pentaphenylruthenocene, [Ru( η5-C 5Ph 5)( η5-C 5H 5)], pentaparatolylruthenocene, [Ru{ η5-C 5( p-MeC 6H 4) 5}( η5-C 5H 5)] and pentaphenylpentamethylruthenocene, [Ru( η5-C 5Ph 5)( η5-C 5Me 5)

Abstract

The preparations of the mixed ligand ruthenocenes [Ru( η 5-C 5R 5)( η 5-C 5H 5)] [R 5=Ph 5 ( 1), Ph 4H ( 2) and ( p-MeC 6H 4) 5 ( 3)] and [Ru( η 5-C 5Ph 5)( η 5-C 5Me 5)] ( 4) are reported. The molecular structures of 1 ( Pbca, a=14.234(3), b=20.276(3), c=20.625(4) Å), 3 ( P1̄, a=19.319(7), b=21.007(7), c=10.436(3) Å, α=103.76, β=95.07(3), γ=112.59(2)°) and 4·H 2O ( P1̄, a=12.145(2), b=12.696(4), c=14.281(2) Å, α=80.41(2), β=66.43(1), γ=62.80(2)°) were determined by single crystal X-ray diffraction studies; the cyclopentadienyl rings in each structure are almost parallel and nearly eclipsed. For 1, 2 and 3, two oxidative processes, but no reductive electrochemical processes, were observed. The precipitated product from the reaction of Ru 3(CO) 12, C 5Ph 5Br and Zn in xylenes yielded, after subsequent reaction with NaBPh 4, [Ru( η 5-C 5Ph 5){ η 6-C 6H 4(CH 3) 2}] +BPh 4 − ( 5).