Formation, Activation and Functionalization of Carbon-Element Bonds by Late Transition Metal Complexes

罗格斯大学的艾伦·戈德曼（Alan Goldman）化学部的这一奖项集中在后过渡金属络合物对C-H键的氧化加成和还原消除。 将阐明决定此类复合物中C-H、C-C、C-X和X-H键加成和消除的热力学、动力学和选择性的因素。 由于不饱和底物插入M-C，M-H和M-X键可能是与C-H活化相关的许多潜在催化循环中最困难的步骤，因此也将研究这些插入。 该方法将基于以下方面的广泛整合：1）新的晚期金属络合物的合成，特别是钳形连接的金属络合物，其提供高稳定性以及以良好控制的方式探索辅助配位基团的变化的能力，同时为底物活化和后续步骤留下开放的配位位点。 2)添加/消除和插入/去插入的机制研究。 3)筛选用于化学计量和催化反应的新络合物。 后者将包括CH和X-H加成到不饱和物（烯烃、炔、CO）和脱氢偶联。 当存在不对称催化的潜力时，手性钳形配合物将被研究。 C-H加成产物的反应性将在所得M-C和M-H键的官能化（例如插入）和C-H加成对远程位点的影响（例如由于甲基化而增加的对同芳族和杂芳族亲核攻击的敏感性）方面进行研究。 4)计算（DFT）的研究将被用来提供合成的线索。计算方法将通过机制和筛选研究进行测试和校准。 新的泛函和基组将被研究以提高预测值，从而提高设计和改进新催化剂的能力。催化C-H键转化的发展，以及C-O和C-F键断裂或形成的反应，在从燃料合成到制药的各个领域具有巨大的潜在影响。 学生和博士后将接受广泛的合成，分析和催化剂设计和开发的原则和策略，包括使用计算方法的培训。 研究生、博士后和本科生将通过与雪佛龙的合作获得工业视角。 每年夏天，通过项目种子计划，高中学生从代表性不足的背景暴露在这一领域的研究，并来到科学作为一个门户网站的机会，而不是一个知识体系被接收。

This award in the Division of Chemistry to Alan Goldman at Rutgers University centers on the oxidative addition and reductive elimination of C-H bonds by late transition metal complexes. The factors that govern the thermodynamics, kinetics and selectivity of C-H, C-C, C-X and X-H bond addition and elimination with such complexes will be elucidated. As the insertion of unsaturated substrates into M-C, M-H, and M-X bonds is likely the most difficult step in many potential catalytic cycles related to C-H activation, these insertions will also be investigated. The approach will be based on the extensive integration of: 1) The synthesis of new late metal complexes, particularly pincer-ligated metal complexes, which offer high stability together with the ability to explore variation of ancillary coordinating groups in a well controlled fashion, while leaving open coordination sites for substrate activation and subsequent steps. 2) Mechanistic studies of addition/eliminations and insertion/de-insertions. 3) Screening new complexes for a broad array of stoichiometric and catalytic reactions. The latter will include additions of CH and X-H to unsaturates (olefins, alkynes, CO), and dehydrocoupling. When the potential for asymmetric catalysis exists, chiral pincer complexes will be investigated. The reactivity of C-H addition products will be investigated with respect to functionalization of the resulting M-C and M-H bonds (e.g. insertions) and for the effect of C-H addition on remote sites (e.g. increased susceptibility toward nucleophilic attack on homo- and heteroaromatics as a result of metallation). 4) Computational (DFT) studies will be used to provide leads for synthesis. Computational methods will be tested and calibrated by mechanistic and screening studies. New functionals and basis sets will be investigated to increase predictive value, and thus the ability to design and improve new catalysts.The development of catalytic C-H bond transformations, as well as reactions in which C-O and C-F bonds are broken or formed, has vast potential impact in areas ranging from the synthesis of fuels to pharmaceuticals. Students and postdoctoral associates will receive broad training in synthesis, analysis, and in the principles and strategy of catalyst design and development, including the use of computational methods. Graduate students, postdoctoral associates and undergraduates will gain industrial perspectives through collaboration with Chevron. Every summer, through the Project SEED program, high school students from under-represented backgrounds are exposed to research in this area and come to view of science as a portal to opportunity rather than a body of knowledge to be received.