1st Row Transition Metal Synthesis and Reactivity Studies Toward Catalysis

康奈尔大学化学与化学生物学系的Peter T. Wolczanski教授将在化学合成项目中探索第一排过渡金属在碳-碳键形成反应、选择性二氮结合反应、碳氢化合物的氧化官能化和金属簇作为潜在的水还原催化剂中的应用。自由基反应是氧化碳氢化合物的一种方法，但这些转化缺乏选择性，限制了它们的应用。这项研究提出了一种控制自由基过程的方法，这种方法将允许进行选择性氧化。此外，不是由碳氢化合物（其主要来源）产生的二氢（H2）是一种很有前途的替代燃料，本研究探索了不同的减水方法作为产生H2的手段。就更广泛的影响而言，拟议的工作可能导致新的C-C键形成工艺，可应用于商品或精细（例如，药物）化学品的合成。碳氢化合物氧化和水裂解是21世纪重要的合成和能源问题。将碳氢化合物直接转化为增值产品具有巨大的能源和成本节约潜力。研究生和本科生将接受各种光谱学、x射线晶体学、动力学和力学评估、分子轨道计算以及处理空气敏感化合物的培训。通过在会议上发表报告，以及通过在五年级和八年级女生中推广科学来传播这项研究。培养能够适应具有挑战性和波动的博士后、学术或工业市场的独立、多才多艺的博士是一个共同的人力资源目标。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Peter T. Wolczanski of the Department of Chemistry and Chemical Biology at Cornell University will explore the utilization of first row transition metals in new carbon-carbon bond forming reactions, selective dinitrogen binding reactions, the oxidative functionalization of hydrocarbons, and metal clusters as potential water reduction catalysts. Radical reactions are one means to oxidize hydrocarbons, but the lack of selectivity in these transformations limits their utility. The research proposed suggests a way of controlling radical processes that will permit selective oxidations to be performed. Furthermore, dihydrogen (H2) that is not produced from hydrocarbons (its predominant source) is a promising alternative fuel, and this research explores different approaches to water reduction as a means to produce H2.In terms of broader impacts, the proposed work could lead to new C-C bond forming processes that can be applied to the synthesis of commodity or fine (e.g., drugs) chemicals. Hydrocarbon oxidation and water splitting are critical synthesis and energy problems of the 21st century. The direct transformation of hydrocarbons to value-added products has the potential for enormous energy and cost savings. Graduate and undergraduate students will be trained in various spectroscopies, X-ray crystallography, kinetics and mechanistic evaluations, molecular orbital calculations as well as in handling air sensitive compounds. Dissemination of this research through presentations at meetings, and via the promotion of science at the 5th-grade level and to 8th grade girls, is included. The production of independent, versatile PhDs capable of adapting to a challenging and fluctuating postdoctoral, academic or industrial market is a concurrent human resource objective.