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Unique Group Transfer and Coupling Reactivity Promoted by Middle and Late Transition Metals in Bulky Alkoxide Ligand Environments

大体积醇盐配体环境中中过渡金属和后过渡金属促进的独特基团转移和偶联反应活性

基本信息

批准号：
1855681
负责人：
STANISLAV GROYSMAN
金额：
$ 45万
依托单位：
Wayne State University
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：
2019-06-15 至 2024-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855681&HistoricalAwards=false
关键词：
Unique Group Transfer Coupling Reactivity

项目摘要

Carbodiimides are a type of molecule that are frequently used in chemical and pharmaceutical industries. Likewise ketenimines are molecular starting points for the production of complicated medicinal chemicals and azoarenes are commonly used dyes in the textile and food industries. While all of these are valuable industrial reagents, a serious disadvantage of all of them is that they are obtained from wasteful processes that involve toxic reagents such as mercury and isocyanate. In order to reduced these problems, the development of new routes to these compounds is an important goal. Dr. Stanislas Groysman, Chemistry Department, Wayne State University and Dr. Richard Lord, Chemistry Department, Grand Valley State University, are supported by the Chemical Synthesis Program of the Chemistry Division to develop new, efficient methods to prepare azoarenes, carbodiimides, and ketenimines. The research develops new cost-effective reagents that exploit metals like iron and cobalt to efficiently produce these molecules. The laboratory experiments are carried out in Dr. Groysman's laboratories and the results are interpreted using computational chemistry conducted by Dr. Lord and his students. Wayne State is a graduate research university, while Grand Valley State is a primarily undergraduate institution. The collaboration provides the opportunity for students from both institutions to be part of both graduate and undergraduate research experiences. The reactivity of metal-bound carbene and nitrene depends on the electronic structure of the metal complex, which is underwritten by the metal type and its ancillary ligand environment. Most existing middle and late nitrene/carbene complexes utilize strong-field ancillary ligands which stabilize formally high-valent metal centers. This project seeks to develop middle and late transition metal complexes featuring weak-field bulky bis(alkoxide) ligation. The electronic properties and the steric bulk of the alkoxide ligands allow the formation of reactive low-coordinate species. The chemistry is explored across the first-row transition metals from Cr to Ni. The effect of the alkoxide ligand field on the electronic structure is explored by computational chemistry. The synthetic work is carried out in the Groysman lab at Wayne State University and the computational work in the Lord lab at Grand Valley State University. This collaboration between a research university and a primarily undergraduate institution provides a valuable experience for students at both institutions.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.

碳二亚胺是一种经常用于化学和制药工业的分子。同样，氯胺酮是生产复杂药用化学品的分子起点，偶氮芳烃是纺织和食品工业中常用的染料。虽然所有这些都是有价值的工业试剂，但它们都有一个严重的缺点，即它们是从涉及汞和异氰酸酯等有毒试剂的浪费过程中获得的。为了减少这些问题，开发这些化合物的新途径是一个重要的目标。Wayne州立大学化学系的Stanislas Groysman博士和Grand Valley州立大学化学系的Richard Lord博士得到化学部门化学合成计划的支持，开发新的，高效的方法来制备偶氮芳烃，碳二酰亚胺和酮胺。该研究开发了新的具有成本效益的试剂，利用铁和钴等金属有效地产生这些分子。实验室实验在格罗伊斯曼博士的实验室进行，结果由洛德博士和他的学生使用计算化学进行解释。韦恩州立大学是一所研究生研究型大学，而大山谷州立大学主要是一所本科院校。此次合作为两所大学的学生提供了参与研究生和本科生研究经历的机会。金属结合的碳和亚硝基的反应性取决于金属配合物的电子结构，这是由金属类型及其辅助配体环境所保证的。大多数现有的中晚期亚硝基/羰基配合物利用强场辅助配体来稳定正式的高价金属中心。本项目旨在开发中后期过渡金属配合物，具有弱场大体积的醇氧基结合体。醇盐配体的电子性质和空间体积允许形成反应性低配位物质。研究了从Cr到Ni的第一排过渡金属的化学性质。用计算化学的方法研究了醇盐配体场对电子结构的影响。合成工作在韦恩州立大学的格罗伊斯曼实验室进行，计算工作在大山谷州立大学的洛德实验室进行。研究型大学和主要本科院校之间的合作为两所院校的学生提供了宝贵的经验。该奖项反映了美国国家科学基金会的法定使命，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

期刊论文数量（12）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Synthesis of Chromium(II) Complexes with Chelating Bis(alkoxide) Ligand and Their Reactions with Organoazides and Diazoalkanes

DOI：
10.3390/molecules25020273
发表时间：
2020-01
期刊：
Molecules
影响因子：
4.6
作者：
Sudheer S. Kurup;R. Staples;Richard L. Lord;Stanislav Groysman
通讯作者：
Sudheer S. Kurup;R. Staples;Richard L. Lord;Stanislav Groysman

Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl 2 (OR) 2 complexes

二聚 Tl 2 (OR) 2 配合物的合成、表征和醇盐转移反应性

DOI：
10.1039/d0dt03917a
发表时间：
2021
期刊：
Dalton Transactions
影响因子：
4
作者：
Grass, Amanda;Kulathungage, Lakshani Wathsala;Wannipurage, Duleeka;Yousif, Maryam;Ward, Cassandra L.;Groysman, Stanislav
通讯作者：
Groysman, Stanislav

Tying the alkoxides together: an iron complex of a new chelating bulky bis(alkoxide) demonstrates selectivity for coupling of non-bulky aryl nitrenes

DOI：
10.1039/c9cc05319k
发表时间：
2019-09-16
期刊：
CHEMICAL COMMUNICATIONS
影响因子：
4.9
作者：
Kurup, Sudheer S.;Wannipurage, Duleeka;Groysman, Stanislav
通讯作者：
Groysman, Stanislav

Simple magnesium alkoxides: synthesis, molecular structure, and catalytic behaviour in the ring-opening polymerization of lactide and macrolactones and for copolymerization of maleic anhydride and propylene oxide

简单醇镁：丙交酯和大环内酯开环聚合以及马来酸酐和环氧丙烷共聚中的合成、分子结构和催化行为

DOI：
发表时间：
2023
期刊：
Dalton transactions
影响因子：
4
作者：
Wannipurage, D.;D’Aniello, S.;Pappalardo, D.;Kulathungage, L. W.;Ward, C. L.;Anderson, D. P.;Groysman, S.;Mazzeo, M.
通讯作者：
Mazzeo, M.

Heterocoupling of Different Aryl Nitrenes to Produce Asymmetric Azoarenes Using Iron–Alkoxide Catalysis and Investigation of the Cis–Trans Isomerism of Selected Bulky Asymmetric Azoarenes