CAS: Development of Multidentate Ligands that Incorporate Metal-Ligand Cooperativity into Catalytic Hydrofunctionalization Reactions

CAS：开发将金属-配体协同作用纳入催化氢官能化反应的多齿配体

• 批准号: 2101002
• 负责人: Christine Thomas
• 金额: $ 49.63万
• 依托单位: Ohio State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2101002&HistoricalAwards=false
• 关键词: CAS; Development; Multidentate; Ligands; Incorporate

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Christine Thomas at Ohio State University is studying the fundamental design of new, more sustainable, catalysts for hydrofunctionalization reactions. Catalytic hydrofunctionalization reactions provide an environmentally friendly method to convert widely available chemical feedstocks into synthetic intermediates that can easily be converted into value-added products with uses in pharmaceuticals, consumer products, and the commodity chemical industry. The project aims to uncover new catalysts that are easily produced from naturally abundant and inexpensive precursors, particularly taking advantage of Earth-abundant metals such as manganese, iron, and cobalt. This project is directly contributing to the rigorous training of both graduate students and undergraduate researchers in preparation for their careers as scientific researchers. In efforts to increase the participation of underrepresented groups in chemistry, Professor Thomas serves as the faculty advisor to the student organization for women in chemistry at Ohio State (Females of Chemistry Uniting Scientists, FOCUS), is an active member of the NOBCChE (National Organization for the Professional Advancement of Black Chemists and Chemical Engineers) Collaborative, and will be launching a new summer undergraduate program in the Ohio State Department of Chemistry and Biochemistry specifically focused on providing research opportunities for underrepresented minority students (CoNQUER, Collaborative NOBCChE Quintessential Undergraduate Experience in Research). With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Christine Thomas at Ohio State University is studying the design of new multidentate ligand frameworks in an effort to promote metal-ligand cooperativity with Earth-abundant first row transition metals (e.g., iron, cobalt, manganese). The project aims to uncover more sustainable catalytic methods by using metal-ligand cooperative processes as a strategy to make and break chemical bonds without relying on two-electron redox cycles that are often inaccessible to first row metals. Ligand design is at the heart of this project, and the Thomas group is evaluating several different approaches in this regard. A tridentate PPP-based pincer ligand featuring an N-heterocyclic phosphide fragment has been shown to actively participate in metal-ligand cooperative reactions in which sigma bonds are cleaved across the metal-phosphide linkage, and ongoing studies focus on the expansion of established stoichiometric reactions and their incorporation into catalytic cycles for the hydroboration, hydrogenation, and hydrosilylation of unsaturated substrates. In addition, Thomas’s research team is exploring a new tetradentate PNNP-based ligand that contains two amide donors as potential sites for metal-ligand cooperativity. The coordination of this ligand to Fe, Co, and Mn and the stoichiometric reactivity of the resulting (PNNP)M compounds towards the activation of substrates such as hydrogen, silanes, and boranes across the two metal-amide bonds is under investigation, with the ultimate goal of incorporating these fundamental reaction steps into catalytic hydrofunctionalization reactions. Lastly, a newly discovered metal-templated procedure for the elimination and substitution of phosphine substituents will be leveraged to synthesize an expanded family of ligands, including tetradentate ligand derivatives that feature both phosphide and amide donors as potential reactive sites, PPP- and PNNP-based ligands with more electron-rich alkyl substituents, and tridentate and tetradentate ligands with P-chiral functionalities for use in asymmetric catalysis. The new synthetic method will provide researchers in the field with a new economical and straightforward method to synthesize large families of multidentate ligand derivatives including P-chiral variants without the need for expensive precursors.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.

在化学系化学催化项目的支持下，俄亥俄州州立大学的克莉丝汀托马斯教授正在研究新的、更可持续的加氢官能化反应催化剂的基本设计。催化加氢官能化反应提供了一种将广泛可用的化学原料转化为合成中间体的环境友好的方法，所述合成中间体可以容易地转化为用于药物、消费品和日用化学工业的增值产品。该项目旨在发现新的催化剂，这些催化剂很容易从天然丰富和廉价的前体中生产出来，特别是利用地球上丰富的金属，如锰，铁和钴。该项目直接有助于对研究生和本科生研究人员进行严格的培训，为他们作为科学研究人员的职业生涯做准备。 在努力增加在化学中的代表性不足的群体的参与，教授托马斯担任教师顾问的学生组织的妇女在化学俄亥俄州国家（化学联合科学家女性，FOCUS），是NOBCChE的积极成员（全国黑人化学家和化学工程师专业促进组织）协作，并将在化学和生物化学的俄亥俄州专门专注于提供研究机会，为代表性不足的少数民族学生（CoNQUER，合作nobcch典型本科生经验的研究）的状态部门推出一个新的夏季本科生计划。 在化学系化学催化计划的支持下，俄亥俄州州立大学的克莉丝汀托马斯教授正在研究新的多齿配体框架的设计，以促进与地球丰富的第一行过渡金属的金属-配体协同性（例如，铁、钴、锰）。 该项目旨在通过使用金属-配体协同过程作为一种策略来发现更可持续的催化方法，以建立和打破化学键，而不依赖于第一行金属通常无法进入的双电子氧化还原循环。配体设计是这个项目的核心，托马斯小组正在评估这方面的几种不同方法。 具有N-杂环磷化物片段的三齿PPP基钳形配体已被证明积极参与金属-配体协同反应，其中σ键在金属-磷化物键上裂解，并且正在进行的研究集中在扩展已建立的化学计量反应及其并入不饱和底物的硼氢化、氢化和硅氢化的催化循环中。 此外，托马斯的研究小组正在探索一种新的四齿PNN基配体，其中含有两个酰胺供体作为金属配体协同作用的潜在位点。该配体的Fe，Co和Mn的配位和所得到的（PNNP）M化合物的化学计量反应性对活化的基板，如氢，硅烷，和硼烷跨越两个金属-酰胺键正在调查中，最终目标是将这些基本的反应步骤催化加氢官能化反应。最后，一个新发现的金属模板程序的消除和取代的膦取代基将被利用来合成一个扩展的家庭的配体，包括四齿配体衍生物，功能磷化物和酰胺供体作为潜在的反应位点，PPP和PNNP为基础的配体与更多的富电子的烷基取代基，和三齿和四齿配体与P-手性功能用于不对称催化。新的合成方法将为该领域的研究人员提供一种新的经济和直接的方法来合成大家族的多齿配体衍生物，包括P-手性变体，而不需要昂贵的前体。该奖项反映了NSF的法定使命，并被认为是值得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的支持。

项目成果

Electronic and Structural Variations of a Nickel(0) N-Heterocyclic Phosphenium Complex in Comparison to Group 10 Analogues

与第 10 族类似物相比，镍 (0) N-杂环磷配合物的电子和结构变化

• DOI: 10.1021/acs.inorgchem.2c03302
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Oliemuller, Leah K.;Moore, Curtis E.;Thomas, Christine M.
• 通讯作者: Thomas, Christine M.

Si–H Bond Activation and Dehydrogenative Coupling of Silanes across the Iron–Amide Bond of a Bis(amido)bis(phosphine) Iron(II) Complex

双(酰胺基)双(膦)铁(II)配合物铁酰胺键上硅烷的Si-H键活化和脱氢偶联

• DOI: 10.1021/jacs.2c12157
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Stevens, Jeremiah E.;Moore, Curtis E.;Thomas, Christine M.
• 通讯作者: Thomas, Christine M.

Catalytic Hydrogenation of Terminal Alkenes by a (PPP) Pincer-Ligated Cobalt(II) Complex

• DOI: 10.1021/acs.organomet.3c00170
• 发表时间: 2023-05
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Matthew C. Fitzsimmons;Azamat Yessengazin;Gillian P. Hatzis;Jeremiah E. Stevens;C. Moore;Christine M. Thomas-Chris