Transition Metal Boryl and Borylidene Complexes: Synthesis and Reactivity of Unusual Metal Ligand Interactions

这个无机、生物无机和有机金属化学项目的奖项支持耶鲁大学化学系的John F. Hartwig博士关于硼基和硼烷取代基的过渡金属配合物的研究。以前还没有制备过硼烷配合物。含有0到8个d电子的多种金属的硼基配合物将使用Hartwig在初步工作中演示的方法合成。这类化合物的结构和反应性尚未得到明确的表征。硼基类化合物与金属催化硼氢化反应密切相关，广泛应用于有机合成，包括立体定向合成。这些化合物可能表现出以前在具有金属碳或金属氧键的相关化合物中未观察到的新反应。在过渡金属和硼原子之间含有一个或两个键的化合物尚未被广泛研究。它们类似于其他含有金属-碳键的化合物，这些化合物被认为是有机反应的有用催化剂。由于含硼化合物的不同电子特性，它们已被证明具有有用的催化性能，但它们的潜力尚未得到充分的探索。Hartwig博士将开发制备金属硼化合物的合成方法，确定它们的结构和基本性质，并测试它们的反应性，特别是与它们作为催化剂的潜在用途有关的反应性。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports study by Dr. John F. Hartwig of the Chemistry Department, Yale University, on transition metal complexes with boryl and borylidene substituents. Borylidene complexes have not previously been prepared. Boryl complexes of a wide variety of metals containing from zero to eight d-electrons will be synthesized using methods demonstrated by Hartwig in preliminary work. Basic information will be compiled on structure and reactivity of this class of compounds which has not been definitively characterized. The boryl species are of direct interest because of their relevance to metal catalyzed hydroboration, which is widely used in organic synthesis, including stereospecific synthesis. These compounds may display novel reactions not previously observed in related compounds with metal carbon or metal oxygen bonds. %%% Compounds which contain one or two bonds between a transition metal and a boron atom have not been extensively studied. They are analogs to other compounds containing metal-carbon bonds which are known to be useful catalysts for organic reactions. Because of the different electronic characteristics of the boron-containing compounds, they have been shown to have useful catalytic properties, but their potential has not been fully explored. Dr. Hartwig will develop synthetic methods for preparing metal-boron compounds, determine their structure and basic properties, and test their reactivity, particularly as related to their potential use as catalysts.