期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 23, 页码 7347-7356出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b01906
关键词
-
资金
- NSF [1058051]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1464538, 1058051] Funding Source: National Science Foundation
We report the crystal structure of a substoichiometric, HMPA-trisolvated lithium pinacolone enolate tetramer (LiOPin)(4)center dot HMPA(3) abbreviated as T-3. In this tetramer One HMPA binds to lithium more strongly than the other two causing a reduction in spatial symmetry with corresponding loss of C-3 symmetry. A variety of NMR experiments, including HMPA titration, diffusion coefficient-formula weight (D-FW) analysis, and other multinuclear one- and two-dimensional NMR techniques reveal that T3 is the major species in hydrocarbon solution when more than 0.6 equiv of HMPA is present. Due to a small amount of moisture from HMPA or air leaking into the solution, a minor complex was identified and confirmed by X-ray diffraction analysis as a mixed aggregate containing enolate, lithium hydroxide, and HMPA in a 4:2:4 ratio, [(LiOPin)(4)center dot(LiOH)(2)center dot HMPA(4)], that we refer to as pseudo-T-4. A tetra-HMPA-solvated lithium cyclopentanone enolate tetramer was also prepared and characterized by X-ray diffraction, leading to the conclusion that steric effects dominate the formation and solvation of the pinacolone aggregates. An unusual mixed aggregate consisting of pinacolone enolate, lithium diisopropyl amide, lithium oxide, and HMPA in described. the ratio 5:1:1:2 is also
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据