Microwave Spectroscopy Measurements of Structures and Electronic Properties of Transition Metal Complexes

过渡金属配合物结构和电子性质的微波光谱测量

• 批准号: 0304969
• 负责人: Stephen Kukolich
• 金额: $ 36.72万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-05-01 至 2007-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0304969&HistoricalAwards=false
• 关键词: Microwave; Spectroscopy; Measurements; Structures; Electronic

In this project, funded by the Experimental Physical Chemistry Program of the Chemistry Division, the PI will study the rotational spectra of transition metal complexes and hydrogen-bonded complexes by microwave spectroscopy. Measurements will be made with a pulsed-beam Fourier-transform spectrometer system constructed at the University of Arizona. A new nozzle system with an electric discharge region will be constructed to work on radicals. The data obtained will be analyzed to determine three-dimensional, gas-phase structures, and other interaction parameters. The overall objectives of this work include the determination of the structures and quadrupole coupling coefficients for: a) dinuclear transition metal complexes; b) weakly-bound complexes with transition metal compounds (models for intermediates in catalyzed reactions); c) hydrogen-bonded base pair analogs; d) structures of complexes involved in methyl migration reactions, and e) structures of organometallic radicals and reaction products. The measured gas-phase structures, which are free from crystal packing distortions or solvent effects, can be directly compared with the theoretical calculations for free molecules. Quantum mechanical (DFT) calculations will be carried out to complement the experimental work done. Graduate and undergraduate students will participate in this research. The results of this work will be of benefit to the chemical industry, which uses transition metal catalysts in the production of chemical products, as well as for the study of biological systems such as many enzymes and transport proteins in living systems that involve transition metal complexes, while details of hydrogen-bonded base pair interactions may be useful in DNA chemistry.

在这个由化学部实验物理化学计划资助的项目中，PI将通过微波光谱学研究过渡金属络合物和氢键络合物的转动光谱。 测量将与脉冲光束傅里叶变换光谱仪系统在亚利桑那大学建造。 一个新的喷嘴系统与放电区将被构造工作的自由基。 将分析获得的数据，以确定三维，气相结构，和其他相互作用参数。 本工作的总体目标包括确定的结构和四极耦合系数：a）双核过渡金属配合物; B）与过渡金属化合物的弱结合配合物（催化反应中的中间体模型）; c）氢键碱基对类似物; d）涉及甲基迁移反应的配合物的结构，和e）有机金属自由基和反应产物的结构。测量的气相结构，这是免费的晶体包装扭曲或溶剂的影响，可以直接与自由分子的理论计算。 将进行量子力学（DFT）计算，以补充所做的实验工作。 研究生和本科生将参与这项研究。这项工作的结果将有利于化学工业，它使用过渡金属催化剂在化学产品的生产，以及生物系统的研究，如许多酶和运输蛋白质在生命系统中，涉及过渡金属络合物，而氢键碱基对相互作用的细节可能是有用的DNA化学。