Structures and Reactions of New Main-Group Organometallic Compounds

这项资助是在有机化学和高分子化学项目中进行的。本研究将研究在一系列标准有机镁试剂中加入高活性有机碳氢阴离子锂盐或碱金属盐对测定结果的影响。当这些化学物种平衡时，会形成一种新的带负电的碳负离子，它表现出极大的化学反应活性。这种动态平衡也可以通过添加冠醚或络合剂来改变，冠醚或络合剂隔离带正电荷的金属离子，导致明显不同的化学行为。具体地说，拟议的研究涉及主族金属的新有机金属物种的制备、结构和反应。这项研究的主要部分将与镁离子有关。这些负的有机镁离子将从普通有机化合物以多种方式合成化合物，包括添加配位剂，如冠醚和密码，或简单的盐，如碱金属醇盐和四烷基卤化铵。将研究镁酸盐物种的结构和反应。镁酸盐离子通常比传统的有机镁化合物活性高得多，并与某些底物提供不同的产物。其他需要合成和结构研究的有机镁物种包括有机镁阳离子(RMG+)和二有机镁化合物(R2 MG)，它们由冠醚等配位基团稳定。拟议工作的一部分还将涉及制备其他金属的新有机金属物种，特别是由带有冠醚的有机铝或有机锌化合物形成的物种。

This grant is in the Organic and Macromolecular Chemistry Program. In this study the influence of the addition of highly reactive lithium or alkali metal salts of organic hydrocarbon anions to a series of standard organomagnesium reagents will be investigated. As these chemical species equilibrate, a new negatively charged carbanion is formed that exhibits greatly enhanced chemical reactivity. This dynamic equilibrium can also be favorably altered by the addition of crown ethers or complexing agents the sequester the positively charged metal ions resulting in markedly different chemical bahavior. Specifically, the proposed research is concerned with preparations, structures, and reactions of new organometallic species of main-group metals. A major portion of the research will concern magnesiate ions. These negative organomagnesium ions will be synthesized from ordinary organic compounds in a number of ways compounds, including addition of coordinating agents, such as crown ethers and cryptands, or simple salts, such as alkali metal alkoxides and tetraalkylammonium halides. Structures and reactions of magnesiate species will be investigated. Magnesiate ions generally are considerably more reactive than conventional organomagnesium compounds and with some substrates furnish different products. Other organomagnesium species to be synthesized and studied structurally include organomagnesium cations (RMg+) and diorganomagnesium compounds (R2Mg) that are stabilized by coordinating groups such as crown ethers. A portion of the proposed work also will involve preparation of new organometallic species of other metals, particularly species formed from organoaluminum or organozinc compounds with crown ethers.