Tridentate Coordination Modes of Functionalized Titanocene Thiolates. Crystal Structure of [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)(2)W(CO)(3)].
Mixed monosubstituted cyclopentadienyl Ti(IV) derivatives [(eta(5)-C(5)H(4)R)(eta(5)-C(5)H(4)SiMe(3))Ti(SPh)(2)] (R = PPh(2), Ph(2)P=O, Ph(2)P=S) react with carbonylmetal fragments of group 6 to generate heterodinuclear compounds [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)(2)M(CO)(3)], [(eta(5)-C(5)H(4)SiMe(3))(SPh)Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)M(CO)(4)], [(eta(5)-C(5)H(4)P(E)Ph(2))(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-SPh)(2)M(CO)(4)] (M = Mo, W; E = O, S) and [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-E-C(5)H(4)P(E)Ph(2))(&mgr;-SPh)(2)M(CO)(3)] (M = Mo, W; E = S or M = Mo, E = O). All complexes have been characterized by spectroscopic data. The crystal structure of [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)(2)W(CO)(3)] has been determined by X-ray diffraction techniques, and it was confirmed that the titanium precursor acts as a tridentate metalloligand. The complex crystallizes in the orthorhombic system in space group Pna2(1); a = 23.081(2) Å, b = 14.3046(9) Å, c = 11.6892(8) Å; Z = 4.
Delgado
Esther
E
Departamento de Química Inorgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid, Spain, and Instituto de Ciencia de Materiales, CSIC, Cantoblanco, 28049 Madrid, Spain.
García
M. Angeles
MA
Gutierrez-Puebla
Enrique
E
Hernández
Elisa
E
Mansilla
Noelia
N
Zamora
Félix
F