Experimental and Computational Studies of Bifunctional Organometallic Catalysis

催化剂（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很大的实际重要性，有助于化学和制药工业的经济可行性，并提供有效利用稀缺资源的新方法。在生物系统中，酶在进行对生命至关重要的化学反应时非常有效。事实上，酶通常比实验室或工业催化剂更有效。正因为如此，它们在设计新催化剂时可以是非常有用的指导。道格拉斯博士B。Grotjahn和Andrew L.圣地亚哥州立大学的Cooksy在化学系化学催化项目的支持下，使用酶启发的设计原理来制备和改进工业过程的催化剂。他们的工作重点是开发新的催化剂，通过不产生废物的途径将天然气中的成分转化为更复杂、更有价值的化学品。该赠款还支持培训催化领域的年轻研究人员。本研究利用酶的设计原理，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。合成含有供质子基团或氢键基团的配体，并与各种金属前体组合以形成金属络合物。与非极性和极性反应物、中间体或过渡态的相互作用产生更快的催化剂。重点主要是无废物加成或异构化反应，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）开发加成反应催化剂;（5）从周期表第一行的廉价金属中创造催化剂。该项目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。拟议的研究为我们的双功能催化图片增加了新的机理见解，使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。为了扩大公众对计算化学的理解，外展计划为8- 12年级的学生提供了3D分子可视化的个性化介绍。课程计划是与教师合作制定的，以反映国家提出的学习目标。研究生为开发催化反应的可视化做出贡献，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。

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.