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

金属-配体键的热化学和碰撞诱导解离的动力学

• 批准号: 9877162
• 负责人: Peter Armentrout
• 金额: $ 59.45万
• 依托单位: University of Utah
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-05-15 至 2002-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9877162&HistoricalAwards=false
• 关键词: Thermochemistry; Metal; Ligand; Bonds; Dynamics

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.

犹他大学的 Peter Armentrout 博士在实验物理化学计划的支持下，利用流动余辉离子产生和引导离子束质谱技术继续进行气相有机金属离子化学和化学动力学研究。 通过精确测量热能和超热能下的绝对反应概率，可以获得详细的动力学和热力学数据。 实验将集中于原子和部分连接的金属离子与一系列中性试剂的反应，重点是较重的（第二行和第三行）过渡金属。 随着过渡金属中心变重，自旋轨道耦合对化学的影响变化的表征特别令人感兴趣。 还将研究连续连接对金属中心热化学和反应性的影响。 这项工作的结果预计将允许气相研究提供的详细信息与凝聚相有机金属和催化反应之间更好的相关性，其中配位不饱和过渡金属中心已知是关键中间体。 了解化学反应产生或所需的能量趋势对于理解和预测各种化学行为非常重要。 本研究成果建立的热化学数据库对化学催化和凝聚相有机金属化学具有有益的影响，具有广泛的工业意义。