Experimental and Computational Studies of Bifunctional Organometallic Catalysis

催化(加速化学反应的物质)参与了大多数化学产品的生产，并使许多化学过程成为可能。因此，发现新的或改进的催化剂具有重要的现实意义，有助于提高化工和制药行业的经济可行性，并为有效利用稀缺资源提供新的途径。在生物系统中，酶在进行对生命重要的化学反应时非常有效。事实上，酶往往比实验室或工业催化剂效率高得多。正因为如此，它们在设计新催化剂时可以成为非常有用的指南。圣地亚哥州立大学的Douglas B.Grotjahn博士和Andrew L.Cooksy博士在化学系化学催化计划的支持下，利用酶启发的设计原则来制备和改进工业过程中的催化剂。他们的工作重点是开发新的催化剂，通过不产生废物的路线将天然气中的组分转化为更复杂、更有价值的化学品。这笔赠款还支持对催化领域的年轻研究人员进行培训。PIs和参与该项目的学生保持着对当地高中的外展计划，以鼓励学生继续他们的科学学习。本研究利用酶设计原理，特别是氢键和质子转移，通过新的机制来加速有机金属催化和反应。合成了含有质子供给基或氢键基团的配体，并与各种金属前体结合形成金属络合物。与非极性和极性反应物、中间体或过渡态的相互作用可产生更快的催化剂。重点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应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)开发用于加成反应的催化剂；(5)用元素周期表第一行较便宜的金属制造催化剂。该项目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。这项拟议的研究为我们的双功能催化图景增加了新的机理洞察力，使用补充的实验和计算研究来设计更好的催化剂和化学过程。为了扩大公众对计算化学的理解，一个外展项目为8-12年级的学生提供了3D分子可视化的个性化介绍。教学计划是与教师合作制定的，以反映国家明确的学习目标。研究生有助于开发催化反应的可视化，并在访问期间作为讨论领导者和导师参与。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。

Catalysis (substances that accelerate chemical reactions) are involved in the production of a majority of chemical products and make many chemical processes possible. Thus, the discovery of new or improved catalysts has great practical importance, contributes to the economic viability of the chemical and pharmaceutical industries, and provides new ways of efficiently using scarce resources. In biological systems enzymes are exceedingly efficient at carrying out chemical reactions that are important to life. In fact, enzymes are often much more efficient than laboratory or industrial catalysts. Because of this they can be very useful guides in the design of new catalysts. Dr. Douglas B. Grotjahn and Dr. Andrew L. Cooksy, San Diego State University, supported by the Chemical Catalysis Program of the Chemistry Division, use enzyme inspired design principles to prepare and improve catalysts for industrial processes. A focus of their work is on new catalysts to convert components found in natural gas to more complex, valuable chemicals by routes that do not generate waste. This grant also supports the training of young investigators in the field of catalysis. The PIs and the students involved in the project maintain an outreach program to local high schools in order to encourage students to continue their study of science.This research uses enzyme design principlse, particularly hydrogen bonding and proton transfer, to accelerate organometallic catalysis and reactions by new mechanisms. Ligands containing proton-donating or hydrogen-bonding groups are synthesized and combined with a variety of metal precursors to form metal complexes. Interactions with nonpolar and polar reactants, intermediates, or transition states create faster catalysts. The focus is mostly on waste-free addition or isomerization reactions, with several goals: (1) apply 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; (4) develop catalysts for addition reactions; (5) create catalysts from cheaper metals of the first row of the periodic table. The project includes significant one-on-one training in modern techniques of organic and organometallic chemistry, including NMR spectroscopy, catalysis screening, and computation. The proposed research adds 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. To broaden public understanding of the computational chemistry an outreach program provides 8-12th graders an individualized introduction to 3D molecular visualization. The lesson plans are developed in partnership with teachers to reflectlearning objectives articulated by the State. Graduate students contribute to developing visualizations of catalytic reactions and participatd as discussion leaders and mentors during the visits.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.