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

罗格斯大学（Rutgers University）的艾伦·戈德曼（Alan Goldman）在化学系的研究重点是晚期过渡金属配合物对碳氢键的氧化加成和还原消除。本文还将阐明影响C-H、C-C、C-X和X-H键加成和消去的热力学、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，因此这些插入也将被研究。该方法将基于以下方面的广泛整合：1)合成新的晚期金属配合物，特别是螯合金属配合物，它具有高稳定性，能够以良好的控制方式探索辅助配位基的变化，同时为底物激活和后续步骤留下开放的配位位点。2)添加/消除和插入/去插入的机理研究。3)为广泛的化学计量和催化反应筛选新的配合物。后者包括CH和X-H对不饱和烃（烯烃、炔烃、CO）的加成和脱氢偶联。当存在不对称催化潜力时，手性钳形配合物将被研究。C-H加成产物的反应性将根据所产生的M-C和M-H键的功能化（例如插入）和C-H加成对远程位点的影响（例如由于金属化而增加对亲核攻击的敏感性）进行研究。计算（DFT）研究将为合成提供线索。计算方法将通过机械和筛选研究进行测试和校准。将研究新的功能和基集，以提高预测价值，从而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，在从燃料合成到药物等领域具有巨大的潜在影响。学生和博士后将在合成、分析、催化剂设计和开发的原则和策略，包括计算方法的使用方面接受广泛的培训。研究生、博士后助理和本科生将通过与雪佛龙的合作获得工业前景。每年夏天，通过Project SEED项目，来自弱势背景的高中生都能接触到这一领域的研究，并逐渐将科学视为通往机会的门户，而不是需要接受的知识体系。

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.