Studies of the Activation and Functionalization of Hydrocarbons at Multinuclear Metal Sites in Transition Metal-Gold Complexes

南卡罗来纳大学化学系和生物化学系的Richard D. Adams教授在化学合成项目资助下，正在开发合成含金的双金属过渡金属团簇配合物的新方法，用于制造碳氢化合物转化和重组的新催化剂。简单的碳氢化合物，如甲烷和乙烷，现在可以从今天丰富的天然气供应中获得。迫切需要开发催化剂，将这些资源有效地转化为高价值的商品化学品。研究将集中于开发用于选择性氧化反应的新催化剂，通过对环境友好的化学过程将简单的碳氢化合物转化为含氧化合物，如醇和羧酸。贵金属元素，如钌、铑、铼、铱和铂，将被研究，因为它们具有众所周知的激活碳氢化合物CH键的能力。金将以化学方式加入到新的催化剂中，因为它最近发现了活化氧并将其转移到碳原子上的能力。更广泛的影响包括开发将天然气和有关资源转化为有价值的化学品的新工艺，这些化学品可用作生产高辛烷值燃料的添加剂和合成新聚合物和材料的原料。研究生和本科生接受最新的科学探究和分析方法的培训，为在学术界或化学工业的职业生涯做准备。含金过渡金属团簇的烃类化合物是由有机金化合物与贵重过渡金属的金属羰基团簇配合物反应制备的。这些异金属团簇配合物转化为双金属和多金属纳米颗粒，用作碳氢化合物选择性氧化的纳米催化剂。控制碳原子上氧的加成是理解金属催化选择性氧化反应本质的核心。机制的研究进行，重点是了解碳氢化合物的CH键的转变的性质，由配合物含有两个或更多的金属原子。这些研究包括对C - O键形成的研究。用x射线衍射和高分辨透射电镜对配合物和催化剂进行了研究。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Richard D. Adams of the Department of Chemistry and Biochemistry at the University of South Carolina is developing new methods for the synthesis of bimetallic transition metal cluster complexes containing gold to be used to create new catalysts for the transformations and reforming of hydrocarbons. Simple hydrocarbons such as methane and ethane are now available from today's abundant supplies of natural gas. There is a great need to develop catalysts to transform these resources efficiently into higher value commodity chemicals. Studies will be focused on the development of new catalysts for selective oxidation reactions that will convert simple hydrocarbons into oxygenated compounds, such as alcohols and carboxylic acids, via environmentally-friendly chemical processes. Precious metal elements, such as ruthenium, rhodium, rhenium, iridium, and platinum will be studied because of their well-known ability to activate the CH bonds of hydrocarbons. Gold will be chemically incorporated into the new catalysts because of its recently discovered ability to active oxygen and transfer it to carbon atoms. Broader impacts include the development of new processes for the conversion of natural gas and related resources into valuable chemicals for use as additives to produce higher octane fuels and for feedstocks for the synthesis of new polymers and materials. Graduate and undergraduate students are trained in the latest methods of scientific inquiry and analysis as preparation for careers in academia or the chemical industry. Hydrocarbyl containing gold-transtion metal clusters are prepared by the reaction of organogold compounds with metal carbonyl cluster complexes of the precious transition metals. These heterometallic cluster complexes are converted into bi- and multimetallic nanoparticles for use as nanocatalysts for the selective oxidation of hydrocarbons. The controlled addition of oxygen to the carbon atoms is central understanding the nature of metal-catalyzed selective oxidation reactions. Mechanistic studies are carried out and focus on understanding the nature of transformations of the CH bonds of the hydrocarbon by complexes containing two or more metal atoms. These studies include investigations of the formation of C - O bonds. The complexes and catalysts are studied by X-ray diffraction and high resolution transmission electron microscopy.