Thermochemistry of Metal-Ligand Bonds and the Dynamics of Collision-Induced Dissociation

犹他大学的Peter Armentrout博士得到了实验物理化学计划的支持，利用流动余辉离子产生和引导离子束质谱仪技术，继续他在气相有机金属离子化学和化学动力学方面的研究。通过准确测量在热能和超热能下的绝对反应几率，将获得详细的动力学和热力学数据。实验将集中在原子和部分配位的金属离子与一系列中性试剂的反应，重点是较重的(第二和第三排)过渡金属。当过渡金属中心变得更重时，自旋-轨道耦合对化学的影响的变化的特征是特别有趣的。还将研究顺序连接对金属中心的热化学和反应性的影响。这项工作的结果有望使从气相研究获得的详细信息与已知配位不饱和过渡金属中心是关键中间体的缩合相有机金属和催化反应之间有更好的相关性。了解进行化学反应所产生或所需能量的趋势，对于理解和预测广泛的化学行为很重要。利用本研究结果建立的热化学数据库对凝聚相中的化学催化和有机金属化学具有重要意义，具有广阔的工业应用前景。

Dr. Peter Armentrout of the University of Utah is supported by the Experimental Physical Chemistry Program to continue his studies of gas phase organometallic ion chemistry and chemical dynamics, utilizing the techniques of flowing afterglow ion production and guided ion beam mass spectrometry. Detailed kinetic and thermodynamic data will be obtained by accurate measurement of absolute reaction probabilities at thermal and hyperthermal energies. Experiments will focus on reactions of atomic and partially-ligated metal ions with a range of neutral reagents, emphasizing heavier (second and third row) transition metals. The characterization of the changing effects of spin-orbit coupling on the chemistry as transition metal centers get heavier is of particular interest. Studies of the effects of sequential ligations on the thermochemistry and reactivity of metal centers will be performed as well. The outcomes from this work are expected to permit better correlations between the detailed information available from gas phase studies and condensed-phase organometallic and catalytic reactions where coordinatively unsaturated transition metal centers are known to be key intermediates. Learning about trends in the energy that is evolved or required to carry out chemical reactions is important for understanding and predicting a wide range of chemical behavior. The thermochemical database that is established with the outcomes of this research has useful impacts in chemical catalysis and organometallic chemistry in condensed phases, with broad industrial implications.