RUI: Unusual Earth-Abundant Metal Complexes with Redox-Active Terpyridine Ligands for Reduction Catalysis

RUI：具有氧化还原活性三联吡啶配体的不寻常的地球丰富金属配合物用于还原催化

• 批准号: 1900500
• 负责人: Guoqi Zhang
• 金额: $ 26.99万
• 依托单位: CUNY John Jay College of Criminal Justice
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900500&HistoricalAwards=false
• 关键词: RUI; Unusual; Earth; Abundant; Metal

In this project, Dr. Guoqi Zhang of John Jay College of the City University of New York is developing new catalysts for the synthesis of silicones. Silicones are important to society as they are typically heat-resistant polymers used in sealants, adhesives, lubricants, medicine, cooking utensils, and thermal and electrical insulation. Silicones are currently industrially made using platinum which is expensive, rare and environmentally-damaging to mine. This research is focusing on replacing platinum with other more Earth-abundant and sustainable metals. Dr. Zhang has designed new families of catalysts using metals such as manganese, vanadium, and aluminum. Catalysts based on these inexpensive metals have traditionally been ignored because they are usually unreactive and unstable. Dr. Zhang is addressing these gaps using group attached to the metal that enhance the reactivity of these metals. This project also provides hands-on training for undergraduate students in both organic chemistry and inorganic chemistry. Experience with modern instrumentation is gained by these students. John Jay College, which has a large Hispanic student population, is an ideal setting to train students who are underrepresented in scientific fields. Dr. Zhang aims to investigate the synthesis, structures and catalytic properties of base metal complexes supported by redox active terpyridine ligands, as well as their catalytic properties relevant to silicone preparation. Novel catalysts composed of Earth-abundant metals including manganese, vanadium and aluminum and terpyridine-type ligands are being explored for their unique structures and catalytic reactivity in reduction processes. Their applications in catalytic hydrofunctionalization reactions are sought to develop effective catalysts to replace platinum-based catalysts that are widely used in industrial silicone production. Mechanistic studies are being carried out based on a combined experimental and theoretical effort, in order to understand the importance of ligand compartment and to establish the structure-activity relationships. Dr. Zhang's active involvement in recruiting and retaining minority students into scientific fields is helping to cultivate the next generation workforce. This project is being done in collaboration with John Jay's Program for Research Initiatives for Science Majors.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.

在这个项目中，纽约城市大学约翰杰伊学院的张国奇博士正在开发用于合成有机硅的新催化剂。 有机硅对社会很重要，因为它们是典型的耐热聚合物，用于密封剂，粘合剂，润滑剂，药品，炊具以及热绝缘和电绝缘。 目前，工业上使用铂制造有机硅，铂价格昂贵、稀有且对矿山环境有害。 这项研究的重点是用其他地球上更丰富和可持续的金属取代铂。 Zhang博士设计了使用锰、钒和铝等金属的新型催化剂系列。基于这些廉价金属的催化剂传统上被忽视，因为它们通常不反应且不稳定。Zhang博士正在使用附着在金属上的基团来解决这些缺口，这些基团可以增强这些金属的反应性。该项目还为有机化学和无机化学的本科生提供实践培训。 这些学生获得了使用现代仪器的经验。 约翰杰伊学院，其中有大量的西班牙裔学生人口，是一个理想的设置，以培养学生谁是在科学领域的代表性不足。Zhang博士的目标是研究氧化还原活性三联吡啶配体负载的贱金属配合物的合成，结构和催化性能，以及它们与有机硅制备相关的催化性能。由锰、钒、铝等地球上丰富的金属和三联吡啶类配体组成的新型催化剂因其独特的结构和在还原过程中的催化活性而受到人们的关注。它们在催化加氢官能化反应中的应用旨在开发有效的催化剂，以取代广泛用于工业有机硅生产的铂基催化剂。机制研究正在进行的基础上结合实验和理论的努力，以了解配体室的重要性，并建立结构-活性关系。张博士积极参与招募和留住少数民族学生进入科学领域，有助于培养下一代劳动力。该项目是与约翰·杰伊的科学专业研究计划合作完成的。该奖项反映了NSF的法定使命，并通过使用基金会的知识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

Correction to “Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C═X (X = O, N) Functionalities”

对“氧化还原非无害配体支持的钒催化剂用于化学选择性还原 C”X (X = O, N) 功能性的修正

• DOI: 10.1021/jacs.0c09331
• 发表时间: 2020
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zhang, Guoqi;Wu, Jing;Zheng, Shengping;Neary, Michelle C.;Mao, Jincheng;Flores, Marco;Trovitch, Ryan J.;Dub, Pavel A.
• 通讯作者: Dub, Pavel A.

Vanadium-Catalyzed Stereo- and Regioselective Hydroboration of Alkynes to Vinyl Boronates

钒催化炔烃立体和区域选择性硼氢化反应生成乙烯基硼酸酯

• DOI: 10.1021/acscatal.2c01318
• 发表时间: 2022
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Zhang, Guoqi;Zeng, Haisu;Zheng, Shengping;Neary, Michelle C.;Dub, Pavel A.
• 通讯作者: Dub, Pavel A.

Vanadium-catalysed regioselective hydroboration of epoxides for synthesis of secondary alcohols

• DOI: 10.1039/d3dt01865b
• 发表时间: 2023-08-08
• 期刊: DALTON TRANSACTIONS
• 影响因子: 4
• 作者: Zhang，Guoqi;Zeng，Haisu;Neary，Michelle C.
• 通讯作者: Neary，Michelle C.

Giant N-heterocyclic carbene-containing macrocycles for cobalt-catalysed hydroboration of alkynes

用于钴催化炔烃硼氢化反应的巨型含氮杂环卡宾大环化合物

• DOI: 10.1039/d2cc02815h
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Zhang, Guoqi

Assembly of a 3D Cobalt(II) Supramolecular Framework and Its Applications in Hydrofunctionalization of Ketones and Aldehydes

• DOI: 10.3390/chemistry4020029
• 发表时间: 2022-04
• 期刊: Chemistry
• 作者: Guoqi Zhang;Alex Wang;Haisu Zeng;Shengping Zheng;Michelle C. Neary