Experimental and Computational Studies of Bifunctional Organometallic Catalysis

在化学系化学催化计划的支持下，圣地亚哥州立大学的道格拉斯·B·格罗特贾恩教授和安德鲁·L·库克西教授正在进行研究，旨在确定新反应的最佳催化剂，这些催化剂可用于制造各种用途的感兴趣的有机化合物，包括制药、材料和生物。为了做到这一点，许多含有金属和更大非金属部分(配体)的催化剂将被制造和测试，以确定什么金属和配体的组合将产生最好的催化剂。此外，还将对催化剂如何在分子水平上运行进行基础研究。这笔赠款将支持对催化领域的几名年轻研究人员的培训。由于催化占全球GDP的三分之一，以及大部分化学产品和化工过程，因此发现新的或改进的有机反应催化剂和新的反应机理具有重要的现实意义，有助于经济发展和复苏。与前一批赠款期间一样，将开发和改进实用的催化剂。此外，为了扩大公众对催化的理解，PIs和研究生将把这个概念引入到一个现有的、非常成功的高中外展项目中。在化学系化学催化项目的支持下，圣地亚哥州立大学的Douglas B.Grotjahn教授和Andrew L.Cooksy教授将利用自然酶的设计原理，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。含有质子供给基或氢键基团的配体将被合成，并与各种金属前驱体结合，形成用于催化的金属衍生物。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有望产生更快的催化剂。重点将主要放在无废物的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基于计算机的分子预测的使用；(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；以及(4)开发用于加成反应的催化剂。该项目将包括在有机和有机金属化学的现代技术方面进行重要的一对一培训，包括核磁共振光谱、催化筛选和计算。拟议的研究将为我们的双功能催化图景增加新的机械洞察力，使用补充的实验和计算研究，以允许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智力优势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.