Catalytic and Catalytically Relevant Formation, Activation and Functionalization of Covalent Bonds by Late Transition Metal Complexes

在这个由化学部化学催化项目资助的项目中，罗格斯大学的Alan Goldman教授正在开发新的催化反应，将分子添加到以前更大、更复杂的分子中。总体目标是开发合成有用和实用的新催化剂和催化过程。Goldman教授也在研究反应机制（即反应如何进行）和控制催化反应化学性质的因素，这将有助于优化催化结果，并增加我们的化学基础知识基础。新的催化转化的发展可能会导致从燃料到塑料到药品等产品的新途径。据估计，催化技术的产品占美国国内生产总值（GDP）的近20%，因此这种新化学的潜在影响可能是广泛的。研究生和本科生在化学合成、表征、机理研究和计算分子设计方面接受广泛的训练，这些对于成功解决任何与催化有关的科学问题都是重要的。该项目的参与者开始与新泽西州泽西城的自由科学中心合作，共同设计一个互动式触摸式展览，供参观者“虚拟合成”常见的家用化学品，如阿司匹林和塑料。最终的计划是将这个展览扩展到其他科学中心，并可能扩展到其他平台，如个人电脑、平板电脑或智能手机。Goldman教授正在研究迟过渡金属催化剂的基本氧化加成和M-X插入反应及其微观逆转。合成了新的SiNP、PC(4-py)P和手性PCP钳形配体，并与铱金属中心络合，研究了烯烃在M-X键上的插入、在C-O键上的裂解和插入以及在芳基C-H键上的正交插入。催化的C-H键功能化常常被这样一个事实所挫败，即潜在的试剂，如一氧化碳结合，强烈地结合在激活C-H键所需的配位位点上。Goldman教授正在研究Bronsted酸如何催化C-H向金属羰基络合物的加成，而金属羰基络合物不容易添加额外的一氧化碳当量。这种化学反应可能是开发碳氢化合物羰基化催化剂的手段。对插入M-X键和C-X加成/消去反应（特别是X = O和N）的基础研究将为开发新的和更有效的这类催化剂提供信息。这种化学最终可能影响商品和精细化学合成技术。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Alan Goldman at Rutgers University is developing new catalytic reactions to add molecules together to former larger, more complex ones. The overall goal is to develop new catalysts and catalytic processes that are both synthetically useful and practical. Professor Goldman is also studying the reaction mechanisms (i.e., how the reactions work) and the factors that control the chemistry of the catalytic reactions, which will help to optimize the outcomes of the catalysis and to add to our fundamental knowledge base about chemistry. The development of new catalytic conversions may lead to new routes to products ranging from fuels to plastics to pharmaceuticals. Products from catalysis technology have been estimated to account for nearly 20% of the U.S. Gross Domestic Product (GDP), so the potential impacts of such new chemistry could be broad. Graduate and undergraduate students are receiving broad training in chemical synthesis, characterization, mechanistic study, and computational molecular design, which are important for success in any scientific problem-solving endeavor related to catalysis. Participants in the project are beginning a collaboration with the Liberty Science Center in Jersey City, NJ to co-design an interactive touch-table exhibit for visitors to "virtually synthesize" common household chemicals such as aspirin and plastics. Eventually the plan is to expand this exhibit to other science centers, and possibly to other platforms such as personal computers, tablets, or smart phones.Professor Goldman is studying fundamental oxidative addition and M-X insertion reactions of late-transition-metal catalysts and their microscopic reverse. New SiNP, PC(4-py)P, and chiral PCP pincer ligands are being synthesized, complexed to iridium metal centers and studied for olefin insertions into M-X bonds, cleavage and insertions into C-O bonds, and ortho-directed insertions into aryl C-H bonds. Catalytic C-H bond functionalization is often frustrated by the fact that potential reagents such as carbon monoxide bind strongly bind to the coordination sites typically required to activate the C-H bond. Professor Goldman is studying how Bronsted acids catalyze C-H addition to metal carbonyl complexes that do not readily add additional equivalents of carbon monoxide. This chemistry potentially is the means to develop a hydrocarbon carbonylation catalyst. Fundamental studies of insertion into M-X bonds and C-X addition/elimination reactions (particularly X = O and N) will inform the development of new and more effective catalysts of this type. This chemistry eventually could impact commodity and fine chemical synthesis technology.