New Aspects of Early d-Block Metal Aryloxide Chemistry

早期 d 区金属芳氧化物化学的新方面

• 批准号: 0078405
• 负责人: Ian Rothwell
• 金额: $ 36万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-08-01 至 2004-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0078405&HistoricalAwards=false
• 关键词: New; Aspects; Early; Block; Metal

Dr. Ian P. Rothwell, Department of Chemistry, Purdue University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division, for research into early transition metal aryloxide chemistry. The central theme of the project involves the use of sterically bulky aryloxide ligation to support both stiochiometeric and catalytic reactivity of unsaturated small molecules at transition metal centers. Studies will aim toward a mechanistic understanding of titanium-aryloxide catalyzed [2+2+1] acetylene trimerization and the development of the synthetic utility of the reaction. New C2 symmetric, chiral aryloxides will be used as monodentate supporting ligands to carry out asymmetric carbon-carbon bond forming reactions. Fundamental studies of the factors controlling both kinetic and thermodynamic resolution of the chiral species will be carried out. Finally, cationic metallacyclic niobium and tantalum complexes will be prepared. Sterically bulky groups bound to transition metals are often effective in preventing reactants of certain size and shape from accessing the metal center. As a consequence, the reactions that do occur produce products with a preferred geometry. In this study, bulky alkoxide groups will be used to effect stereospecific reactivity to some early transition metal promoted reactions of utility in the synthesis of organic compounds.

普渡大学化学系的Ian P. Rothwell博士得到了化学系无机，生物无机和有机化学计划的支持，研究早期过渡金属芳氧化物化学。该项目的中心主题涉及使用空间庞大的芳氧基连接，以支持不饱和小分子在过渡金属中心的化学计量和催化反应性。研究的目的是对钛-芳氧基催化的[2+2+1]乙炔三聚反应的机理的理解和发展的反应的合成效用。新的C2对称的手性芳氧化物将被用作单齿支持配体来进行不对称碳-碳键形成反应。将进行控制手性物质的动力学和热力学拆分的因素的基础研究。最后，将制备阳离子金属环铌和钽配合物。与过渡金属键合的空间大体积基团通常有效地与过渡金属键合。 防止一定尺寸和形状的反应物接触金属 中心 因此，确实发生的反应产生具有优选几何形状的产物。 在这项研究中，庞大的醇盐基团将被用来影响立体特异性的反应，一些早期的过渡金属促进的反应，在有机化合物的合成中的效用。