SusChEM: Tools for the Development of High-Valent Transition Metal Catalysts

SusChEM：开发高价过渡金属催化剂的工具

• 批准号: 1562140
• 负责人: Aaron Odom
• 金额: $ 44.3万
• 依托单位: Michigan State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1562140&HistoricalAwards=false
• 关键词: SusChEM; Tools; Development; Valent; Transition

In this project funded by the Chemical Catalysis Program of the Chemistry Division of the National Science Foundation, Professor Aaron Odom and coworkers at Michigan State University are developing a new method to predict how the rates of chemical reactions can be enhanced to lower energy consumption and provide more specific control of large scale chemical production. The Odom group is exploring multicomponent coupling catalysis as a means of lowering the time and energy required to access more complex chemical products in greater yield. Their method focuses on the use of early transition metals like titanium and zirconium, which are earth-abundant and offer unique chemical products. By understanding and systematizing the factors that control the reactivity of these catalysts, the time and effort required for catalyst optimization is minimized. Catalyst optimization is explored in systems that show promise for a multicomponent, one-pot method of generating a variety of different important heterocyclic cores commonly employed in pharmaceuticals. Graduate and undergraduate students participate in the research, learning the principles of inorganic/organometallic chemistry and chemical experimentation. The method for ligand parameterization relies on readily synthesized chromium(VI) nitrido complexes, where the estimated enthalpic barrier to rotation around the chromium center serves as a measure of donor ability through competition for acceptor orbitals on the metal between the amido nitrogen lone pair and donation (sigma and pi) from the donor ligand. The new parameter measured by spin saturation transfer in the 1H NMR spectra has been dubbed the Ligand Donor Parameter (LDP). In preliminary studies, the ligand descriptor LDP has been applied to titanium-catalyzed hydroamination of alkynes with primary amines. The effect of the ancillary ligands on the titanium catalysis can be effectively modeled using LDP for the electronic component and percent buried volume for the steric descriptor. The method allows the prediction of reaction rates prior to catalyst synthesis, the identification of systems that undergo side reactions or catalyst degradation, and, in some cases, the determination of catalytic intermediates. In this research project, the parameters are being expanded to new ligand types. Additional methods of modeling catalysis involving more diverse ligand types are also being explored.

在这个由国家科学基金会化学部化学催化计划资助的项目中，密歇根州立大学的Aaron Odom教授和同事正在开发一种新方法来预测如何提高化学反应的速率以降低能耗，并为大规模化学生产提供更具体的控制。 Odom集团正在探索多组分偶联催化，以降低获得更复杂化学产品所需的时间和能量。 他们的方法侧重于使用早期过渡金属，如钛和锆，这些金属在地球上储量丰富，并提供独特的化学产品。通过了解和系统化控制这些催化剂反应性的因素，可以最大限度地减少催化剂优化所需的时间和精力。 催化剂的优化系统中进行了探索，显示出一个多组分的承诺，一锅法产生的各种不同的重要的杂环核心常用的药物。研究生和本科生参加研究，学习无机/有机金属化学和化学实验的原则。配体参数化的方法依赖于容易合成的铬（VI）次氮配合物，其中估计的围绕铬中心旋转的焓垒通过酰氨基氮孤对和捐赠之间对金属上受体轨道的竞争来衡量供体能力（sigma和pi）来自供体配体。在1H NMR谱中通过自旋饱和转移测量的新参数被称为配体供体参数（LDP）。在初步研究中，配体描述符LDP已被应用于钛催化的炔与伯胺的氢胺化反应。辅助配体对钛催化的影响可以有效地使用LDP的电子组件和空间描述符的百分比掩埋体积建模。该方法允许在催化剂合成之前预测反应速率，识别经历副反应或催化剂降解的系统，并且在某些情况下，测定催化中间体。在该研究项目中，参数正在扩展到新的配体类型。 涉及更多样化的配体类型的建模催化的其他方法也正在探索中。