Synthesis, Structure, and Reactivity of the Sterically Crowded Complex (C5Me4SiMe3)3U

被引：10
作者：
Siladke, Nathan A. [1 ]
Ziller, Joseph W. [1 ]
Evans, William J. [1 ]
机构：
[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
来源：
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2010年 / 636卷 / 13-14期
基金：
美国国家科学基金会;
关键词：
Cyclopentadienyl ligands; Metallocenes; THF ring-opening; Steric crowding; Uranium; H BOND ACTIVATION; (C5ME5)(3)M COMPLEXES; LIGANDS; HALIDES; RADII; ALKYL; LN;
D O I：
10.1002/zaac.201000225
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The unusual chemistry obtainable from sterically crowded (C5R5)(3)M complexes has been explored with M = U and (C5Me4SiMe3)(1), a ligand that has independently provided unexpected uranium chemistry. (C5Me4SiMe3)(2)UMe2. (1), is reduced by potassium to generate the "ate" salt (C5Me4SiMe3)(2)UMe2K (2), which reacts with [HNEt3][BPh4] to yield the cationic species [(C5Me4SiMe3)(2)U][BPh4] (3). KC5Me4SiMe3 reacts with 3 in benzene to form (C5Me4SiMe3)(3)U, (4). The structure of 4 shows that the displacement of the methyl groups from the cyclopentadienyl ring planes, a useful indicator of steric crowding, is the largest ever observed in a (C5R5)(3)M complex. The reactivity of 4 is consistent with this structural indicator in that it engages in THF ring opening to form (C5Me4SiMe3)(2)UO[(CH2)(4)(C5Me4SiMe3)](THF).
引用
收藏
页码：2347 / 2351
页数：5
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