Structural studies of mono(pentamethylcyclopentadienyl)lanthanide complexes
Titel:
Structural studies of mono(pentamethylcyclopentadienyl)lanthanide complexes
Auteur:
Evans, William J. Champagne, Timothy M. Davis, Benjamin L. Allen, Nathan T. Nyce, Gregory W. Johnston, Matthew A. Lin, Ying-Chih Khvostov, Alex Ziller, Joseph W.
Verschenen in:
Journal of coordination chemistry
Paginering:
Jaargang 59 (2006) nr. 10 pagina's 1069-1087
Jaar:
2006-07-10
Inhoud:
The mono(pentamethylcyclopentadienyl) lanthanide complexes [(C5Me5)Yb(μ-I)(μ-η5 : η5-C5Me5)Yb(C5Me5)]n (1), {[(C5Me5)Sm]3(μ-Cl)4(μ3-Cl)(μ3-OH)(THF)}2 (2), {[(C5Me5)Sm]2 (μ-OH)(μ-Cl)4(μ3-Cl)Mg(THF)2}2 (3), [(C5Me5)2Sm](μ-Cl)6(μ3-Cl)2(μ4-Cl)[(C5Me5)Sm]4 (4), {[(C5Me5)Nd]3(μ3-Cl)4(μ4-Cl)2(μ3-O2CPh)2K2(η6-C7H8)}2 (5), [(C5Me5)Nd(C8H8)]2(μ-dioxane) (6), [(C5Me5)Yb(MeOtBu)]2(μ-η8 : η8-C8H8) (7), [(C5Me5)Dy(μ-I)2]3 (8), and [(C5Me5) Tm(MeCN)6]I2 (9), have been identified by X-ray crystallography. 1 is unusual in that it has a μ-η5 : η5-C5Me5 ring that generates a local bent metallocene environment around ytterbium. Complexes 2-5 demonstrate the versatility of bridging chlorides in generating a variety of structures for mono(pentamethylcyclopentadienyl) lanthanide halides. Complex 6 shows how dioxane can generate a crystallographically-analyzable complex by bridging two mixed-ligand metallocene units that do not readily crystallize with THF. The structure of 7 shows how methyl tert-butyl ether (MTBE) ligates a lanthanide. Complex 8 is a trimeric cyclopentadienyl lanthanide halide unusual in that it has six bridging halides that roughly define a trigonal prism. Complex 9 constitutes an organometallic example of a lanthanide in which acetonitrile completely displaces iodide counterions.