NSF Young Investigator: Transition Metal Complexes with Optically Active Pyrazolyl Ligands

NSF 青年研究员：具有光学活性吡唑基配体的过渡金属配合物

• 批准号: 9357171
• 负责人: William Tolman
• 金额: $ 31.25万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-08-01 至 1999-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9357171&HistoricalAwards=false
• 关键词: NSF; Young; Investigator; Transition; Metal

Proposal: 9357171 PI: Tolman Professor Tolman, of the University of Minnesota, will investigate the transition metal coordination compounds with the assistance of an NSF Young Investigator Award from the Inorganic, Bioinorganic, and Organometallic Chemistry Program. His research program is focussed on two subjects, which are linked by their use of pyrazolyl ligands. One of the projects will use these ligands to prepare copper compounds that can interact with oxonitrogen compounds such as NO; the objective is to use simple coordination chemistry to enhance our understanding of the role of copper in enzymatic denitrification. The other project will use chiral versions of these ligands to bind metal ions in a chiral 3-fold environment; it is anticipated that such metal centers will be able to mediate stereoselective reactions in ways that differ significantly from the more usual chiral 2-fold metal centers. %%% The presence of metal ions in molecules can endow these molecules with unusual properties. A real-world example is found in certain bacterial enzymes, where copper ions lead to the conversion of nitrite to gases such as N2; this particular reaction is a major component of the global nitrogen cycle. The underlying chemistry of copper-nitrogen compounds is presently very poorly understood. With this grant, simple molecules containing copper and various nitrogenous components will be prepared, and their reactions will be studied. Another example of unusual metal ion behavior is the ability of molecules containing metal ions to have the property of chirality (i.e., handedness), and thereby to catalyze important reactions to give only one of a variety of possible products. This grant will enable studies of such systems where the chirality is based on a three-fold symmetry about the metal ion, rather than the more unusual two-fold symmetry. It is expected that this change of symmetry will lead to substantial differences in catalytic activity, poten tially of industrial benefit.

提案：9357171 PI：Tolman 明尼苏达大学的托尔曼教授将在无机，生物无机和有机化学计划的NSF青年研究者奖的帮助下研究过渡金属配位化合物。 他的研究计划集中在两个主题上，这两个主题通过使用吡唑基配体而联系起来。 其中一个项目将使用这些配体来制备可以与NO等氧氮化合物相互作用的铜化合物;目标是使用简单的配位化学来增强我们对铜在酶促脱氮中作用的理解。 另一个项目将使用这些配体的手性版本在手性3重环境中结合金属离子;预计这些金属中心将能够以与更常见的手性2重金属中心显著不同的方式介导立体选择性反应。 分子中金属离子的存在可以赋予这些分子不寻常的性质。 一个真实的例子是在某些细菌酶中发现的，其中铜离子导致亚硝酸盐转化为N2等气体;这种特殊的反应是全球氮循环的主要组成部分。 铜氮化合物的基本化学性质目前还知之甚少。 有了这项资助，将制备含有铜和各种含氮成分的简单分子，并研究它们的反应。 不寻常的金属离子行为的另一个例子是含有金属离子的分子具有手性性质的能力（即，手性），从而催化重要的反应，只得到多种可能产物中的一种。 这项拨款将使研究这些系统的手征是基于一个关于金属离子的三重对称，而不是更不寻常的二重对称。 预期这种对称性的改变将导致催化活性的显著差异，潜在的工业利益。