官能化钛茂硫醇盐的三齿配位模式。[(η(5)-C(5)H(4)SiMe(3))Ti(μ-η(5):κ-P-C(5)H(4)PPh(2))(μ-SPh)(2)W(CO)(3)]的晶体结构

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)].

作者信息

Delgado Esther, García M. Angeles, Gutierrez-Puebla Enrique, Hernández Elisa, Mansilla Noelia, Zamora Félix

机构信息

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.

出版信息

Inorg Chem. 1998 Dec 28;37(26):6684-6689. doi: 10.1021/ic9804972.

DOI:10.1021/ic9804972

PMID:11670799

Abstract

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.

摘要

混合单取代环戊二烯基钛（IV）衍生物[（η⁵-C₅H₄R）（η⁵-C₅H₄SiMe₃）Ti（SPh）₂]（R = PPh₂，Ph₂P=O，Ph₂P=S）与第6族的羰基金属片段反应生成异双核化合物[（η⁵-C₅H₄SiMe₃）Ti（μ-η⁵：κ-P-C₅H₄PPh₂）（μ-SPh）₂M（CO）₃]、[（η⁵-C₅H₄SiMe₃）（SPh）Ti（μ-η⁵：κ-P-C₅H₄PPh₂）（μ-SPh）M（CO）₄]、[（η⁵-C₅H₄P（E）Ph₂）（η⁵-C₅H₄SiMe₃）Ti（μ-SPh）₂M（CO）₄]（M = Mo，W；E = O，S）以及[（η⁵-C₅H₄SiMe₃）Ti（μ-η⁵：κ-E-C₅H₄P（E）Ph₂）（μ-SPh）₂M（CO）₃]（M = Mo，W；E = S或M = Mo，E = O）。所有配合物均通过光谱数据进行了表征。通过X射线衍射技术测定了[（η⁵-C₅H₄SiMe₃）Ti（μ-η⁵：κ-P-C₅H₄PPh₂）（μ-SPh）₂W（CO）₃]的晶体结构，并证实钛前体充当三齿金属配体。该配合物在正交晶系中结晶，空间群为Pna2（1）；a = 23.081（2）Å，b = 14.3046（9）Å，c = 11.6892（8）Å；Z = 4。