Experimental and Computational Studies of Bifunctional Organometallic Catalysis

在化学系化学催化项目的支持下，道格拉斯教授B。Grotjahn和Andrew L.圣地亚哥州立大学的Cooksy正在进行研究，旨在确定新反应的最佳催化剂，这些反应可用于制造各种应用的有机化合物，包括制药，材料和生物学。为了实现这一点，将制备和测试许多含有金属和较大非金属部分（配体）的催化剂，以确定金属和配体的组合将产生最佳性能的催化剂。此外，将进行催化剂如何在分子水平上运作的基础研究。这笔赠款将支持在催化领域培训几名年轻的研究人员。由于催化占全球GDP的三分之一，占化学产品和化学过程的大多数，因此发现新的或改进的有机反应催化剂和新的机理具有很大的实际意义，有助于经济发展和复苏。与上一个赠款期一样，将开发和改进实用催化剂。此外，为了扩大公众对催化的理解，PI和研究生将把这个概念引入一个现有的和非常成功的高中推广计划。在化学系化学催化计划的支持下，道格拉斯教授B。Grotjahn和Andrew L.圣地亚哥州立大学的Cooksy将利用自然界酶的设计原理，特别是氢键和质子转移，通过新的机制加速（通常超过1000倍）有机金属催化和反应。含供质子或氢键基团的配体将被合成，并与各种金属前体结合形成其金属衍生物用于催化。这些侧基与非极性和极性反应物、中间体或过渡态的相互作用预期产生更快的催化剂。重点将主要放在无废物加成或异构化反应上，有几个目标：（1）在催化剂发现之前和之后整合使用基于计算机的分子预测;（2）建立和应用烯烃异构化催化剂工具箱;（3）使用配体使X-H活化;（4）开发加成反应催化剂。该项目将包括有机和有机金属化学现代技术的重要一对一培训，包括NMR光谱学，催化筛选和计算。该研究计划将为我们的双功能催化研究增添新的机理见解，利用互补的实验和计算研究来设计更好的催化剂和化学过程。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professors Douglas B. Grotjahn and Andrew L. Cooksy of San Diego State University are performing research aimed at determining the best catalysts for new reactions that can be used to make organic compounds of interest for a variety of applications, including pharmaceuticals, materials, and biology. To accomplish this, many catalysts that contain a metal and a larger non-metal portion (ligand) will be made and tested, to determine what combinations of metals and ligands will yield the best performing catalysts. In addition, fundamental studies of how the catalysts operate on the molecular level will be performed. This grant will support the training of several young investigators in the field of catalysis. Because catalysis accounts for a third of global GDP and a majority of chemical products and chemical processes, the discovery of new or improved catalysts for organic reactions and new mechanisms has great practical importance, contributing to economic development and recovery. As in the previous grant period, practical catalysts will be developed and improved. Also, to broaden public understanding of catalysis, the PIs and the graduate students will introduce the concept into an existing and highly successful high school outreach program.With the support of the Chemical Catalysis Program in the Division of Chemistry, Professors Douglas B. Grotjahn and Andrew L. Cooksy of San Diego State University will employ design principles of Nature’s enzymes, particularly hydrogen bonding and proton transfer, to accelerate (often by more than 1000-fold) organometallic catalysis and reactions by new mechanisms. Ligands containing proton-donating or hydrogen-bonding groups will be synthesized and combined with a variety of metal precursors to form their metal derivatives for catalysis. Interactions of these pendant groups with nonpolar and polar reactants, intermediates, or transition states are expected to create faster catalysts. The focus will be mostly on waste-free addition or isomerization reactions, with several goals: (1) integrate the use of computer-based molecular predictions before and after catalyst discovery; (2) build and apply a toolbox of alkene isomerization catalysts; (3) use ligands to enable X-H activation; and (4) develop catalysts for addition reactions. The project will include significant one-on-one training in modern techniques of organic and organometallic chemistry, including NMR spectroscopy, catalysis screening, and computation. The proposed research will add new mechanistic insight to our picture of bifunctional catalysis, using complementary experimental and computational studies to allow the design of better catalysts and chemical processes.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.