Cyclopentadienyl-ruthenium and -osmium chemistry
1989; Elsevier BV; Volume: 359; Issue: 3 Linguagem: Inglês
10.1016/0022-328x(89)88099-4
ISSN1872-8561
AutoresMichael I. Bruce, Marie P. Cifuentes, Michael R. Snow, Edward R. T. Tiekink,
Tópico(s)Carbon dioxide utilization in catalysis
ResumoExchange of tertiary phosphites for PPh3 in RuCl(PPh3)2(η-C5H5) afforded RuCl{P(OR)3}2(η-C5H5) (R3 Me3, (CH2CF3)3, (CH2)3CEt). Conventional reactions of the P(OMe3) complex afforded RuX{P(OMe)3}2(η-C5H5 (X = H, C(CO2Me)CH(CO2Me), SnCl3, C2Ph, CCPhC(CN)2C(CN)2, C{C(CN)2}-CPHC(CN)2 (red and yellow forms)) or [Ru(L){P(OMe)3}2(η-C5H5)]+] [L = NCMe, C CHPh, C(OMe)CH2Ph, CCMePh, CCClPh). The phenylethynyl complex was converted to two copper-containing complexes by coordination of CuCl or Cu+ to the C triple bond. Crystals of RuCl{P(OMe)3}2(η-C5H5) are orthorhombic, space group Pna21 with unit cell dimensions a 9.606(3), b 14.167(4) and c 12.891(4) Å and Z = 4; Ru{C[C(CN)2]CPhC(CN)2}{P(OMe)3}2(η-C5H5 exists as two isomers: yellow form, triclinic, space group PI, a 9.496(6), b 10.436(6), c 15.216(2) Å, α 90.74(2), β 90.22(3), γ 111.47(4)° and Z = 2; red form, orthorhombic, space group Pbca, a 14.501(5), b 15.047(2), c 26.658(4) Å and Z = 4. The structures were each refined by a full-matrix least-squares procedure to final R = 0.051, Rw = 0.050 for 1419 reflections with I > 2.5σ(I) for RuCl{P(OMe)3}2(η-C5H5; R = 0.037, Rw = 0.041 for 2930 reflections for the yellow isomer of Ru{C[C(CN)2]CPhC(CN)2}{P(OMe)3}2(η-C5H5); and R = 0.033, Rw = 0.035 for 1661 reflections for the red isomer.
Referência(s)