CAREER: Synthesis and characterization of manganese complexes toward earth-abundant green catalysts

职业：锰配合物的合成和表征，用于地球丰富的绿色催化剂

• 批准号: 1847933
• 负责人: David Lacy
• 金额: $ 65万
• 依托单位: SUNY at Buffalo
• 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: 2019-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1847933&HistoricalAwards=false
• 关键词: CAREER; Synthesis; characterization; manganese; complexes

Chemical reactions are often inefficient, that is, they require considerable energy, or produce undesirable byproducts. Many industrial and laboratory reactions utilize catalysts - substances that lower the energy required for a reaction and/or guide the course of the reaction to specific products. As many current catalysts require the incorporation of expensive and/or toxic metals, the development of new catalysts based on inexpensive, abundant, and non-toxic replacements is an important goal. To this end, Professor David Lacy in the Chemistry Department at the University at Buffalo is supported by the Chemical Synthesis Program of the Chemistry Division to synthesize and characterize new manganese catalysts. Manganese (Mn) is abundant and non-toxic, but is understudied compared to other metals. In this project a series of of reactive maganese complexes are prepared and their basic reactions explored. Based on these results new manganese catalysts for a variety of processes are designed. The project also contains an integrated educational component that emphasizes hands-on experiences for high school students in the local area. This effort aims to assist local schoolteachers in stimulating student enthusiasm in science. Manganese(I) catalysts are currently used in acceptorless (de)hydrogenations with ligand platforms initially designed for ruthenium, but not optimally suited for Mn(I). This project focuses on the preparation of a new library of ligands designed to leverage the special properties of Mn(I). These new ligands include phenol-based phosphines (POP and PO), new PNN and PNP pincer ligands, amino acid-derived chiral PN ligands, and thiophenol-based PS and PSP phosphines. In addition to the synthesis of Mn(I) complexes with these ligands, this research also addresses the lack of Mn(I) catalyst precursors by providing new Mn(I) synthons and/or methods to prepare Mn(I) catalysts from cheaper materials. The electronic properties and decomposition pathways of the Mn(I) complexes and the mechanisms of catalysis are explored to assist robust Mn(I) catalyst design.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.

化学反应通常效率低下，即它们需要相当大的能量或产生不良的副产品。许多工业和实验室反应都利用催化剂 - 降低反应所需的能量和/或指导对特定产品的反应过程。 由于当前许多催化剂都需要掺入昂贵和/或有毒的金属，因此基于廉价，丰富和无毒的替代品的新催化剂的开发是一个重要目标。为此，布法罗大学化学系的David Lacy教授得到了化学综合计划的支持，以合成和表征新的锰催化剂。锰（MN）丰富且无毒，但与其他金属相比被研究了。在这个项目中，准备了一系列反应性玛格纳斯络合物，并探索了它们的基本反应。基于这些结果，设计了用于各种过程的新型锰催化剂。该项目还包含一个综合的教育组成部分，该组成部分强调了当地高中生的动手体验。这项努力旨在帮助当地的学校老师刺激学生对科学的热情。锰（i）催化剂目前用于最初是为氟芬设计的配体平台的受体（DE）氢化中，但不适合Mn（i）。该项目着重于准备新的配体库，旨在利用MN（i）的特殊特性。这些新的配体包括基于苯酚的磷（POP和PO），新的PNN和PNP钳子配体，氨基酸衍生的手性PN配体以及基于硫酚的PS和PSP磷。除了与这些配体合成Mn（I）复合物外，这项研究还通过提供新的MN（I）合成子和/或方法来准备Mn（I）的催化剂前体，以准备MN（I）从廉价材料中催化剂。探索了MN（I）配合物的电子性能和分解途径以及催化机制，以帮助强大的MN（I）催化剂设计。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优点和更广泛影响的审查标准来通过评估来通过评估来支持的。

项目成果

Hydrogenative Catalysis with Three‐Coordinate Zinc Complexes Supported with PN Ligands is Enhanced Compared to PNP Analogs

与 PNP 类似物相比，PN 配体支持的三配位锌配合物的氢化催化性能得到增强

• DOI: 10.1002/chem.202201042
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Paul, Sanchita;Morgante, Pierpaolo;MacMillan, Samantha N.;Autschbach, Jochen;Lacy, David C.
• 通讯作者: Lacy, David C.

Reversible Photoisomerization in a Ru cis -Dihydride Catalyst Accessed through Atypical Metal–Ligand Cooperative H 2 Activation: Photoenhanced Acceptorless Alcohol Dehydrogenation

通过非典型金属配体协同 H 2 活化实现 Ru 顺式二氢化物催化剂中的可逆光异构化：光增强无受体醇脱氢

• DOI: 10.1021/acs.organomet.1c00648
• 发表时间: 2022
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Fanara, Paul M.;Vigneswaran, Vipulan;Gunasekera, Parami S.;MacMillan, Samantha N.;Lacy, David C.
• 通讯作者: Lacy, David C.

Dinuclear Mn(I) Complexes with Phosphido and Hydrido Bridges: Synthesis, Reactivity, and Hydrogenative Catalysis

具有磷脂桥和氢桥的双核 Mn(I) 配合物：合成、反应性和氢化催化

• DOI: 10.1002/chem.202300518
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Lacy, David C.;Abhyankar, Preshit C.
• 通讯作者: Abhyankar, Preshit C.

Synthesis of a Bench-Stable Manganese(III) Chloride Compound: Coordination Chemistry and Alkene Dichlorination

实验室稳定的氯化锰 (III) 化合物的合成：配位化学和烯烃二氯化

• DOI: 10.1021/jacs.2c08509
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Saju, Ananya;Griffiths, Justin R.;MacMillan, Samantha N.;Lacy, David C.
• 通讯作者: Lacy, David C.

H 2 Activation across Manganese(I)–C Bonds: Atypical Metal–Ligand Cooperativity in the Aromatization/Dearomatization Paradigm

锰(I)-C键上的H 2 活化：芳构化/脱芳构范式中的非典型金属-配体协同性

• DOI: 10.1021/acs.organomet.1c00606
• 发表时间: 2022
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Vigneswaran, Vipulan;Abhyankar, Preshit C.;MacMillan, Samantha N.;Lacy, David C.
• 通讯作者: Lacy, David C.