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

犹他州大学的Peter Armentrout博士得到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技术继续研究气相有机金属离子化学和化学动力学。 详细的动力学和热力学数据将通过精确测量热能和超热能下的绝对反应概率来获得。 实验将侧重于原子和部分连接的金属离子与一系列中性试剂的反应，强调较重（第二和第三行）的过渡金属。 随着过渡金属中心变得更重，自旋轨道耦合对化学的变化影响的表征特别令人感兴趣。 也将研究顺序连接对金属中心的热化学和反应性的影响。 这项工作的结果预计将允许更好的相关性的详细信息，从气相研究和凝聚相的有机金属和催化反应，其中协调不饱和过渡金属中心是已知的关键中间体。 了解进行化学反应所产生或所需的能量趋势对于理解和预测广泛的化学行为非常重要。 利用本研究成果建立的热化学数据库在凝聚相化学催化和有机金属化学中具有有用的影响，具有广泛的工业意义。

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.