The Preparation and Study of Novel Receptor Systems

9224686 Thummel这项研究的重点是证明精心设计的基于简单桥联氮杂芳基及其过渡金属络合物的受体系统可以用于实现有用的化学。基于吡嗪的桥联配体提供了将两种金属络合的机会，使得金属配位球中的底物分子可以相互作用，并提供了光氧化还原催化从水中生成氧气的结构途径。简单易得的主体分子已被证明是很好的尿素结合剂，将被用来固定碳酸和氨基甲酸，使它们成为有用的合成中间体。精心剪裁的宿主将被制备成模拟尿素酶的形式，以催化尿素的水解和尿素的形成。最后，二茂铁核将被用作“可变铰链”，它可以控制两个环戊二烯上取代基的相对取向。有了这个奖项，合成有机计划支持休斯顿大学化学系的兰道夫·P·图梅尔博士的研究。Thummel教授将把他的工作重点放在证明精心设计的受体系统可以用于完成有用的化学。氮杂芳基配体及其过渡金属络合物将被用来催化水中氧的光氧化还原生成，固定化碳酸和氨基甲酸使其成为有用的合成中间体，以及作为模拟尿素的尿素水解酶。***

9224686 Thummel The focus of this research is the demonstration that carefully designed receptor systems, based on simple bridged azabiaryls and their transition metal complexes, can be employed to accomplish useful chemistry. Pyridazine based bridging ligands offer the opportunity to complex two metals such that substrate molecules in the coordination sphere of the metal can interact with one another and provide structural access to the photoredox catalyzed generation of oxygen from water. Simple and very accessible host molecules, which have been shown to be excellent urea binders, will be used to immobilize carbonic and carbamic acids to render them useful as synthetic intermediates. Carefully tailored hosts will be prepared as a urease mimic to catalyze the hydrolysis of urea and for the formation of ureaphanes. Finally, the ferrocene nucleus will be employed as a "variable hinge" in which the relative orientation of substituents on the two cyclopentadienyl rings can be controlled. %%% With this award, the Synthetic Organic Program is supporting the research of Dr. Randolph P. Thummel of the Department of Chemistry at the University of Houston. Professor Thummel will focus his work on demonstrating that carefully designed receptor systems can be employed to accomplish useful chemistry. Azabiaryl ligands and their transition metal complexes will be used to catalyze the photoredox generation of oxygen from water, to immobilize carbonic and carbamic acids to render them useful as synthetic intermediates, and to be a urease mimic to hydrolyze urea. ***