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，更复杂的分子中。 总的目标是开发新的催化剂和催化工艺，既综合有用的和实用的。 戈德曼教授也在研究反应机制（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的结果，并增加我们关于化学的基础知识。 新的催化转化技术的发展可能会为从燃料到塑料再到药品等产品开辟新的路线。据估计，来自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，这对于任何与催化有关的科学问题解决奋进的成功都很重要。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，供游客“虚拟合成”阿司匹林和塑料等常见家用化学品。最终计划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。戈德曼教授正在研究后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。 新的SiNP、PC（4-py）P和手性PCP钳形配体正在合成，与铱金属中心络合，并研究烯烃插入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键官能化通常由于潜在试剂如一氧化碳强烈结合到活化C-H键通常所需的配位位点的事实而受阻。戈德曼教授正在研究布朗斯台德酸如何催化C-H加成到金属羰基络合物中，而金属羰基络合物不容易添加额外当量的一氧化碳。这种化学方法可能是开发烃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）的基础研究将为开发这种类型的新的和更有效的催化剂提供信息。 这种化学最终可能会影响商品和精细化学品合成技术。

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.