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Synthesis of Silyl- and Germyl-substituted Borates and their Application to Catalytic Reactions

甲硅烷基和甲锗烷基取代硼酸酯的合成及其在催化反应中的应用

基本信息

批准号：
15550041
负责人：
MOCHIDA Kunio
金额：
$ 2.37万
依托单位：
Gakushuin University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550041/
关键词：
silylborate germyiborate X-ray diffraction analysis group 14 element ketone nucleophile photochemical reaction CIDEP triplet state 求核剤構造触媒反応

项目摘要

Silylborats, (Li[Ph_nMe_<3-n>SiBPh_3], n = 1-3), and germylborates, (Li[Ph_nMe_<3-n>GeBPh_3], n = 1-3) and (E[Et_3GeBPh_3], E = Li, Na, K), were prepared by the reaction of the corresponding silyl- and germylalkali metals with triphenylborane in a hexane/benzene mixed solvent The silyl- and germylborates were fully identified by ^1H, ^<13>C, ^<11>B, and ^7Li NMR spectroscopic methods. Germylborates, Li[Ph_3GeBPh_3] and E[Et_3GeBPh_3] (E = Li and Na), were also determined by X-ray diffraction analyses. The polymeric structure of E[Et_3GeBPh_3] was observed in the solid state and in a hydrocarbon solvent. The alkali metal atoms were located near the center of the benzene ring of triphenylborane and interacted with the neighboring borate molecules by the Li^+-π interaction. The polymeric structure was destroyed by the addition of MeOH, however, E[Et_3GeBPh_3] was coordinated by three MeOH molecules to form the dimeric structure without methanolysis reaction. The primary processes in photochemical reactions of silyl- and germylborates were investigated by chemical trapping experiments and CIDEP method. The cleavage of Ge-B (or Si-B) bonds of germylborates (or silylborates) was most probably considered to occur from their triplet states.

在<3-n><3-n>正己烷/苯混合溶剂中，通过甲硅烷基和甲锗烷基碱金属与三苯基硼烷反应，合成了甲硅烷基硼酸盐（Li [Ph_nMe_ SiBPh_3]，n = 1-3）和甲锗烷基硼酸盐（Li [Ph_nMe_ GeBPh_3]，n = 1-3）和甲锗烷基硼酸盐（E[Et_3GeBPh_3]，E = Li，Na，K）<13><11>。锗基硼酸盐Li[Ph_3GeBPh_3]和E[Et_3GeBPh_3]（E = Li和Na）也用X-射线衍射分析确定。E[Et_3GeBPh_3]在固态和烃类溶剂中均具有聚合结构。碱金属原子位于三苯硼烷苯环中心附近，与相邻的硼酸盐分子通过Li^+-π相互作用。MeOH的加入破坏了聚合物的结构，但E[Et_3GeBPh_3]与三个MeOH分子配位形成二聚体结构，而没有发生甲醇解反应。用化学捕获实验和CIDEP方法研究了甲硅烷基硼酸酯和甲锗烷基硼酸酯光化学反应的主要过程。锗基硼酸盐（或硅基硼酸盐）的Ge-B（或Si-B）键断裂最可能被认为是从它们的三重态发生的。

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Tris(trimethylsilyl)-substituted heavy group 14 element-centered anions : Un-solvated trimeric germyllithium and solvated dimeric silyl-and stannyllithiums

三（三甲基甲硅烷基）取代的重族 14 元素中心阴离子：非溶剂化三聚甲锂和溶剂化二聚甲硅烷基锂和甲锡基锂

DOI：
发表时间：
2004
期刊：
Eur.J.Inorg.Chem.
影响因子：
0
作者：
H.Ikeda;K.Akiyama;Y.Takahashi;T.Nakamura;S.Ishizaki;Y.Shiratori;H.Ohaku;J.L.Goodman;A.Houman;D.D.M.Wayner;S.Tero-Kubota;T.Miyashi;H.Ikeda et al.;南条真佐人
通讯作者：
南条真佐人

Tris (trimethylsilyl)-substituted Heavy Group 14-element Centered Anions : Unsolvated Trimeric Germyllithium and Solvated Dimeric Silyl- and Stannyllithiums

三（三甲基甲硅烷基）取代的重族 14 元素中心阴离子：未溶剂化的三聚甲锗烷基锂和溶剂化的二聚甲硅烷基锂和甲锡烷基锂