Experimental and Theoretical Studies of Bifunctional Organometallic Catalysis

凭借这一奖项，化学部的化学合成项目资助了圣地亚哥州立大学化学与生物化学系的Grotjahn和Cooksy教授，以利用仿生设计原理开发新的有机金属催化剂。提出的双功能催化剂利用了后过渡金属和能够质子转移或氢键的基团的反应活性。含有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金属配合物。加成反应和异构化反应是研究的重点，因为它们是原子经济和无浪费的。合作团队将确定配合物的性质，以解释它们如何发挥催化剂的作用。结合核磁共振和红外光谱、动力学和x射线晶体学，研究了催化活性和非催化活性配合物的配位、氢键供体和接受特性。使用密度泛函理论的反应势能面图将模拟反应机制，特别注意氢键或质子转移的作用以及反应动力学的配体依赖性。这项工作对催化剂设计领域有潜在的更广泛的影响。该方法的成功开发可能会对制药和农业工业的合成产生影响，并可能有助于提高效率和因此更环保的过程。其他更广泛的影响包括培训本科生、研究生和博士后研究人员设计、制造和测试有机化合物和催化剂。此外，为了突出催化的本质和重要性，参与该项目的SDSU学生将与Cooksy一起前往当地学校，在那里他们将向学生介绍分子结构和键的3D可视化。

With this award, the Chemical Synthesis Program of the Chemistry Division is funding Professors Grotjahn and Cooksy of the Department of Chemistry and Biochemistry at San Diego State University to use biomimetic design principles in developing new organometallic catalysts. Proposed bifunctional catalysts use reactivity of both a late transition metal and a group capable of proton transfer or hydrogen bonding. Ligands containing proton-donating or hydrogen-bonding groups will be synthesized and combined with a variety of metal precursors to form metal complexes. Addition and isomerization reactions are the focus of the research, because they are atom-economical and waste-free. The collaborative team will determine properties of complexes to explain how they function as catalysts. The coordination, hydrogen-bond donating and accepting properties of both catalytically active and inactive complexes will be studied by a combination of NMR and IR spectrometry, kinetics, and X-ray crystallography. Maps of the reaction potential energy surfaces using density functional theory will model the reaction mechanisms, with particular attention paid to the role(s) of hydrogen bonding or proton transfer and the ligand dependence of the reaction kinetics. There are potential wider implications of this work for the field of catalyst design. Successful development of the methodology would likely have an impact on synthesis in the pharmaceutical and agricultural industries, and may contribute to more efficient and hence greener processes. Other broader impacts involve training undergraduate students, graduate students and postdoctoral researchers in designing, making and testing organic compounds and catalysts. Moreover, in outreach efforts to highlight the nature and importance of catalysis, SDSU students participating in the project will travel with Cooksy to local schools, where they will introduce students to 3D visualization of molecular structure and bonding.