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非常实际的重要性，有助于化学和制药行业的经济可行性，并提供有效利用稀缺资源的新方法。在生物系统中，在进行对生命重要的化学反应方面非常有效。实际上，酶通常比实验室或工业催化剂要高得多。因此，它们在设计新催化剂的设计中可能非常有用。圣地亚哥州立大学的Douglas B. Grotjahn博士和Andrew L. Cooksy博士在化学部的化学催化计划的支持下，使用酶启发的设计原理来为工业过程准备和改善催化剂。他们的工作重点是新的催化剂，将天然气中发现的组件转换为不产生废物的路线的更复杂，有价值的化学物质。该赠款还支持催化领域的年轻研究人员的培训。 PIS和参与该项目的学生维持了向当地高中的外展计划，以鼓励学生继续学习科学。这项研究使用酶设计的原理，尤其是氢键和质子转移，以加速有机金属催化和通过新机制进行反应。合成含有质子或氢键基的配体含有质子或氢键组的配体，并与多种金属前体合成以形成金属络合物。与非极性和极性反应物，中间体或过渡状态的相互作用会产生更快的催化剂。重点主要放在无废物添加或异构化反应上，其目标是：（1）在发现催化剂之前和之后应用基于计算机的分子预测； （2）构建并应用一个烯烃同组化催化剂的工具箱； （3）使用配体启用X-H激活； （4）开发添加反应的催化剂； （5）从周期表的第一行的较便宜金属中创建催化剂。该项目包括有机和有机化学现代技术的一对一培训，包括NMR光谱，催化筛查和计算。拟议的研究使用互补的实验和计算研究为我们的双功能催化的图片增添了新的机械见解，以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至12年级的人提供了一个个性化的3D分子可视化介绍。该课程计划是与教师合作制定的，以反映国家阐明的目标。研究生在访问期间作为讨论领导者和导师的催化反应和参与者的可视化做出贡献。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的评估评估的评估来支持的。

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.