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

在这个由化学系化学催化计划资助的项目中，罗格斯大学的艾伦·戈德曼教授正在开发新的催化反应，将分子添加到以前更大、更复杂的分子上。总体目标是开发既可用于合成又实用的新催化剂和催化工艺。戈德曼教授还在研究反应机理(即反应如何工作)和控制催化反应化学的因素，这将有助于优化催化结果，并增加我们的化学基础知识。新催化转化器的开发可能会带来从燃料到塑料再到制药等各种产品的新途径。据估计，催化技术的产品占美国国内生产总值(GDP)的近20%，因此这种新化学物质的潜在影响可能是广泛的。研究生和本科生正在接受化学合成、表征、机械研究和计算分子设计方面的广泛培训，这些对于成功解决与催化有关的任何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，共同设计一个互动触摸台展览，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，计划将这一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。戈德曼教授正在研究晚过渡金属催化剂的基本氧化加成反应和M-X插入反应及其微观反转。新的SiNP，PC(4-py)P和手性PCP钳形配体正在被合成，它们被络合到Ir金属中心，并研究了烯烃插入M-X键，裂解和插入C-O键，以及邻位定向插入芳基C-H键。催化C-H键功能化经常受阻于潜在的试剂，如一氧化碳，强烈结合到通常需要激活C-H键的配位位置。戈德曼教授正在研究Bronsted酸如何催化不容易增加一氧化碳当量的金属羰基络合物的C-H加成反应。这种化学有可能成为开发碳氢化合物羰基化催化剂的手段。插入M-X键和C-X加成/消除反应(特别是X=O和N)的基础研究将有助于开发这种类型的新的和更有效的催化剂。这种化学最终可能会影响大宗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.