Microwave Measurements of Structures and Other Properties of Transition Metal Complexes

亚利桑那大学的Stephen Kukolich在实验物理化学项目的支持下，对过渡（TM）氢化物、金属-烯烃配合物、非刚性配合物、双核配合物和有机金属自由基进行了高分辨率傅立叶变换微波（FTMW）光谱研究。在第一种情况下，将研究含有两个氢原子的TM配合物，着眼于区分“二氢”配合物（氢氢键保持完整）和二氢化物（氢原子独立地与金属结合，并且相隔更大的距离）。数据分析将提供三维结构，内部运动，四极耦合常数和偶极矩的研究分子的信息。大多数将被研究的系统被选择来帮助建模和理解催化和酶系统中过渡金属的化学和相互作用。金属氢化物通常具有很强的活性，在许多工业过程中起着重要作用。烯烃与金属络合时的电子和结构变化在催化过程中起着重要作用。大部分工业化学品的有效生产取决于一种或多种催化过程。许多酶的活性位点是生命系统所必需的，涉及各种过渡金属配合物。

Stephen Kukolich of The University of Arizona is supported by the Experimental Physical Chemistry Program to perform high resolution fourier-transform microwave (FTMW) spectroscopic studies of transition (TM) hydrides, metal-olefin complexes, non-rigid complexes, dinuclear complexes and organometallic radicals. In the first case, TM complexes containing two hydrogen atoms will be investigated, with an eye towards distinguishing between `dihydrogen` complexes (the hydrogen-hydrogen bond remains intact) versus dihydrides (hydrogen atoms bond independently to the metal, and are separated by much larger distances). Data will be analyzed to provide information on the three-dimensional structures, internal motion, quadrupole coupling constants and dipole moments of the molecules under study. Most of the systems that will be investigated were chosen to help in modeling and understanding the chemistry and interactions of transition metals in catalytic and enzyme systems. Metal hydrides are often quite reactive and play important roles in many industrial processes. The electronic and structural changes in olefins on complexation to metals play an important part in catalytic processes. Efficient production of a large fraction of industrial chemicals depends on one or more catalytic processes. The active sites of many enzymes which are essential for living systems involve various transition metal complexes.