Structural studies of mono(pentamethylcyclopentadienyl)lanthanide complexes.

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.

The mono(pentamethylcyclopentadienyl) lanthanide complexes [(C 5 Me 5 )Yb( μ -I)( μ - η 5   : η 5 -C 5 Me 5 )Yb(C 5 Me 5 )] n (1), {[(C 5 Me 5 )Sm] 3 ( μ -Cl) 4 ( μ 3 -Cl)( μ 3 -OH)(THF)} 2 (2), {[(C 5 Me 5 )Sm] 2 ( μ -OH)( μ -Cl) 4 ( μ 3 -Cl)Mg(THF) 2 } 2 (3), [(C 5 Me 5 ) 2 Sm]( μ -Cl) 6 ( μ 3 -Cl) 2 ( μ 4 -Cl)[(C 5 Me 5 )Sm] 4 (4), {[(C 5 Me 5 )Nd] 3 ( μ 3 -Cl) 4 ( μ 4 -Cl) 2 ( μ 3 -O 2 CPh) 2 K 2 ( η 6 -C 7 H 8 )} 2 (5), [(C 5 Me 5 )Nd(C 8 H 8 )] 2 ( μ -dioxane) (6), [(C 5 Me 5 )Yb(MeO t Bu)] 2 ( μ - η 8   :   η 8 -C 8 H 8 ) (7), [(C 5 Me 5 )Dy( μ -I) 2 ] 3 (8), and [(C 5 Me 5 ) Tm(MeCN) 6 ]I 2 (9), have been identified by X-ray crystallography. 1 is unusual in that it has a μ - η 5   :   η 5 -C 5 Me 5 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.

RARE earth metals; HALIDES; BUTYL methyl ether; DIOXANE; X-ray crystallography; METALLOCENES

Journal of Coordination Chemistry, 2006, Vol 59, Issue 10, p1069

0095-8972

Academic Journal

10.1080/00958970500512831