Experimental and Computational Studies of Bifunctional Organometallic Catalysis

双功能有机金属催化的实验和计算研究

• 批准号: 1800598
• 负责人: Douglas Grotjahn
• 金额: $ 54万
• 依托单位: San Diego State University Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-01 至 2022-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800598&HistoricalAwards=false
• 关键词: Experimental; Computational; Studies; Bifunctional; Organometallic

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.

催化（加速化学反应的物质）参与大多数化学产品的生产，并使许多化学过程成为可能。因此，新的或改进的催化剂的发现具有重大的实际意义，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，酶在进行对生命重要的化学反应方面非常有效。事实上，酶通常比实验室或工业催化剂更有效。正因为如此，它们可以成为新催化剂设计中非常有用的指南。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项目的支持下，利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型催化剂，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。这笔赠款还支持催化领域年轻研究人员的培训。参与该项目的 PI 和学生在当地高中开展推广计划，以鼓励学生继续进行科学研究。该研究利用酶设计原理，特别是氢键和质子转移，通过以下方式加速有机金属催化和反应：新机制。合成含有供质子或氢键基团的配体，并与各种金属前体结合形成金属配合物。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。重点主要是无浪费的加成或异构化反应，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) 烯烃异构化催化剂工具箱的构建和应用； (3)使用配体使X-H活化； (4) 开发加成反应催化剂； (5)用元素周期表第一行的较便宜的金属制造催化剂。该项目包括重要的有机和有机金属化学现代技术的一对一培训，包括核磁共振波谱、催化筛选和计算。拟议的研究为我们的双功能催化图景增添了新的机制见解，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。为了扩大公众对计算化学的理解，一项外展计划为 8 至 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，以反映国家制定的学习目标。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智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Catalyst versus Substrate Control of Forming ( E )-2-Alkenes from 1-Alkenes Using Bifunctional Ruthenium Catalysts

使用双功能钌催化剂从 1-烯烃形成 (E)-2-烯烃的催化剂与底物控制

• DOI: 10.1021/acs.oprd.8b00315
• 发表时间: 2018
• 期刊: Organic Process Research & Development
• 影响因子: 3.4
• 作者: Paulson, Erik R.;Delgado, Esteban;Cooksy, Andrew L.;Grotjahn, Douglas B.
• 通讯作者: Grotjahn, Douglas B.

Influence of Carbene and Phosphine Ligands on the Catalytic Activity of Gold Complexes in the Hydroamination and Hydrohydrazination of Alkynes

• DOI: 10.1021/acscatal.0c01352
• 发表时间: 2020-03
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: S. Yazdani;Glen P. Junor;Jesse L. Peltier;M. Gembicky;Rodolphe Jazzar;D. Grotjahn;G. Bertrand

X-ray crystallography and electrochemistry reveal electronic and steric effects of phosphine and phosphite ligands in complexes RuII(κ4-bda)(PR3)2 and RuII(κ3-bda)(PR3)3 (bda = 2,2′-bipyridine-6,6′-dicarboxylato)

X 射线晶体学和电化学揭示了配合物 RuII(γ4-bda)(PR3)2 和 RuII(γ3-bda)(PR3)3 (bdaầ=ầ2,2â) 中膦和亚磷酸酯配体的电子和空间效应

• DOI: 10.1016/j.poly.2018.12.033
• 发表时间: 2019
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Yazdani, Sima;Silva, Braden E.;Cao, Thomas C.;Rheingold, Arnold L.;Grotjahn, Douglas B.
• 通讯作者: Grotjahn, Douglas B.