Organometallic Reactivity of Metallomacrocyclic Complexes

在化学部无机、生物无机和有机金属计划的这个项目中，Wayland将继续他对Rh(II)和Ir(II)大环配合物的有机金属反应性的研究。这些基础研究的长期目标是提供适当的金属络合物设计，将简单的碳氢化合物转化为更有用的化合物。主要目标将是从根本上理解第9组金属大循环所观察到的反应性的热力学和动力学-机械基础。重点将放在考察烷烃和一氧化碳与Rh(II)和Ir(II)卟啉的反应。在设计金属络合物时，将同时使用热力学和力学准则，以扩大反应范围和产生反应选择性。主要的长期目标包括系统地使用配体和金属变化来调节热力学因素，以及设计为特定反应提供过渡态预组织的配体系统。

In this project in the Inorganic, Bioinorganic, and Organo- metallic Program of the Chemistry Division, Wayland will continue his studies of the organometallic reactivity of macrocyclic complexes of Rh(II) and Ir(II). These fundamental studies have the long range goal of providing proper design of metal complexes that will convert simple hydrocarbons into more useful compounds. A primary objective will be to achieve a fundamental under- standing of the thermodynamic and kinetic-mechanistic basis for the observed reactivity of Group 9 metallomacrocycles. The focus will be on examining reactions of alkanes and carbon monoxide with Rh(II) and Ir(II) porphyrins. Both thermodynamic and mechanistic criteria will be used in designing metal complexes for the purpose of expanding the range of reactivity and producing reaction selectivity. Major long range goals include the systematic use of ligand and metal variation to tune thermodynamic factors and design of ligand systems that provide preorganization of the transition states for specific reactions.