Synthesis and reactivity of a tethered diene cyclopentadiene, (C5Me4H)SiMe2(CH2CH=CHCH=CH2), and its alkali metal salts

被引:9
|
作者
Evans, WJ [1 ]
Giarikos, DG [1 ]
Ziller, JW [1 ]
机构
[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
关键词
cyclopentadienyl; tethered diene; tetramethylcyclopentadienyl; bent metallocene; potassium; titanium;
D O I
10.1016/j.jorganchem.2003.09.013
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
(C5Me4H)SiMe2Cl reacts with (THF)KCH2CH=CHCH=CH2 to form (C5Me4H)SiMe2(CH2CH=CHCH=CH2) (1). Compound 1 reacts with KH and n-BuLi to make M(C5Me4)SiMe2(CH2CH=CHCH=CH2), M = K, 2; Li, 3, respectively. Carbon-silicon cleavage occurs when I reacts with K to form (C5Me4H)K, which crystallizes from dimethoxyethane as [(C5Me4H)K(DME)](x). This potassium salt has an extended structure which generates bent metallocene (C5Me4H)(2)K(DME) sub-structures which have 133.9degrees ring centroid-K-ring centroid angles. Compound 1 reacts with TiCl4 to make (C5Me4H)TiCl3 (5), which has a piano stool structure. (C) 2003 Elsevier B.V. All rights reserved.
引用
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页码:200 / 205
页数:6
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