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Thermochemical and Reactivity Studies of Basic Transition Metal Complexes

碱性过渡金属配合物的热化学和反应性研究

基本信息

批准号：
8719744
负责人：
Robert Angelici
金额：
$ 21.35万
依托单位：
Iowa State University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1987
资助国家：
美国
起止时间：
1987-12-01 至 1991-11-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=8719744&HistoricalAwards=false
关键词：
Thermochemical Reactivity Studies Basic Transition

项目摘要

This project is in the general area of inorganic chemistry and in the specific area of organometallic chemistry of transition metals. The project is concerned with the tendency of transition metal complexes to act as bases, i.e. to accept protons from other molecules in solution. Such proton transfer reactions are often involved in reactions in which these complexes function either as homogeneous catalysts or as intermediates in the synthesis of complicated organic molecules. Consequently, systematic measurements of their basicities are essential both to understanding reaction mechanisms and to optimizing reaction conditions for using these complexes in organic synthesis. The basicities of a broad range of transition metal complexes will be determined by measuring their heats of protonation. The electronic and steric effects of ligands on complex basicity will be determined by examining values of heat of protonation for a series of complexes with various P-donor and other ligands. In order to understand how metal complex basicities influence other types of complex reactivity, rates of a variety of oxidative-addition reactions will be determined and correlated with heats of protonation. The resulting linear free energy correlations are expected to be useful guides to understanding a broad range of complex reactivity. In related studies heats of protonation will be determined for reactions in which a series of di- and polynuclear metal-metal bonded complexes are converted to H-bridged products. The latter experiments will quantitate the effects of ligands and metals on the basicities of metal-metal bonds.

该项目是在无机化学的一般领域，在过渡金属有机化学的特定领域，金属.该项目关注的是过渡金属配合物作为碱，即接受溶液中其他分子的质子。这种质子转移反应通常涉及这些反应，络合物作为均相催化剂或复杂有机合成中间体分子。因此，系统测量其碱性对于理解反应机理和优化反应条件，这些化合物在有机合成中。各种过渡金属配合物的碱性将通过测量它们的质子化热来确定的配体的电子和空间效应对络合物碱度的影响将通过检查质子化热的值来确定对于一系列具有各种P-供体和其它配体。为了了解金属络合物的碱性影响其他类型的复杂反应性，将确定氧化加成反应，与质子化热有关。由此产生的线性自由能源相关性预计将是有用的指南，了解广泛的复杂反应性。在相关研究质子化热将被确定为反应其中一系列双核和多核金属-金属键合络合物转化为H-桥连产物。后者实验将量化配体和金属的影响，金属-金属键的碱性