Synthesis and characterization of sterically hindered group IV metallocenes

被引:31
|
作者
Grimmond, BJ [1 ]
Corey, JY [1 ]
Rath, NP [1 ]
机构
[1] Univ Missouri, St Louis, MO 63121 USA
关键词
D O I
10.1021/om9808615
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three new Ct symmetric heteroannular dialkyl substituted group IV metallocene dichlorides (Cp-R)(2)MCl2 [Cp-R = C5H4C(Me)(2)CHMe2; M = Zr (2), Hf (3), Ti (4)] were synthesized as potential, catalytic precursors for the dehydropolymerization of silanes to polysilanes. The hindered complexes were generated in fair yield by reaction of 2 equiv of the alkyllithium reagent (CpLi)-Li-R (1) and the corresponding metal halide, MCl4. 2THF for 2 and 3 and MCl3. 3THF for 4. Crystal structures for compounds 2-4 were obtained and established a pseudotrans configuration of the ancillary ligands in the solid state. The structural features adopted by these compounds to accommodate the large substituents are described with comparisons to known metallocenes. Monoalkyl-substituted metallocenes Cp(Cp-R)MCl2, M = Ti (5), Zr (6), were also synthesized from 1 and the corresponding monocylopentadienyl-trihalide species CpMCl3. Characterization of 2-6 by various NMR techniques in conjunction with solid-state analysis of 2, 3, and 4 permitted interpretation of an interligand mechanism for the observed NOE signals involving the distal protons of the substituted cyclopentadienyl ligand and portions of the alkyl cyclopentadienyl substituent.
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页码:404 / 412
页数:9
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