Ligand effects on reactivity of hydride-decorated and reduced multi-iron compounds

配体对氢化物修饰和还原多铁化合物反应活性的影响

基本信息

批准号：
10093066
负责人：
Leslie Justin Murray
金额：
$ 27.69万
依托单位：
UNIVERSITY OF FLORIDA
依托单位国家：
美国
项目类别：
财政年份：
2017
资助国家：
美国
起止时间：
2017-04-01 至 2023-01-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/10093066
关键词：
Active Sites Address Adopted Ammonia Binding Biochemical Reaction Biological Biology Carbon Dioxide Carbon monoxide dehydrogenase Catalysis Chemicals Chemistry Cobalt Competence Complex Data Dioxygen Electrons Elements Enzyme Reactivation Enzymes Face Goals Investigation Ions Iron Iron Compounds Knowledge Learning Life Ligands Light Mediating Metals Molecular Conformation Molybdenum Molybdoferredoxin Nickel Nitrogen Nitrogenase Organism Oxidation-Reduction Pathway interactions Pharmacologic Substance Photosynthesis Process Protons Reaction Research Respiration Role Side Site Structure Sulfides Uncertainty Water Zinc Cluster biological systems cofactor design diazene electronic structure flexibility functional group interstitial metal complex novel strategies oxidation preference protonation public health relevance small molecule spectroscopic data

项目摘要

Title: Ligand effects on reactivity of hydride-decorated and reduced multi-iron compounds Abstract Metal cluster cofactors provide substrates with many potential orientations to bind and subsequently undergo chemical transformations. This is particularly true for cluster cofactors that activate small molecule substrates. The focus of this proposal is on the chemistry of the iron-molybdenum cofactor in the molybdenum-dependent nitrogenases, which catalyzes the eight electron and eight proton reduction of dinitrogen and two protons to generate two equivalents of ammonia and one of dihydrogen. The current mechanism proposed for the conversion of N2 to NH3 by this enzyme uses concepts that are common to numerous other metal cofactors, such as the protonation of bridging sulfide donors, the use of metal hydrides to store reducing equivalents, and the potential to coordinate the hydrides and dinitrogen in either terminal or bridging modes. How the iron-molybdenum cofactor binds hydride donors and dinitrogen, as well as intermediates during the catalytic reaction, are fundamental aspects of the mechanism but remain unclear. This is the knowledge gap that this proposal addresses. This proposal will accomplish this goal by using synthetic clusters in which substrates (hydrides and dinitrogen) can bind in either bridging or terminal coordination modes, which mirrors the coordinative flexibility possible for these substrates on the iron-molybdenum cofactor. As part of this inquiry, this proposal will dissect how number, identity, and connectivity of bridging ligands modulate substrate coordination. The results generated in this proposal have broader implications for biochemical reactions, and specifically, shed light on the principles that govern biological catalysis of multi-electron multi-proton redox reactions (e.g., water oxidation in photosynthesis, dioxygen reduction in respiration).

标题：配体对氢化物装饰和还原的多铁化合物反应性的影响抽象的金属簇辅因子为底物提供许多潜在的方向，以结合并随后进行化学转化。对于激活小的群集辅助因子尤其如此分子底物。该提议的重点是在铁 - 溶血辅因子的化学上钼依赖性氮酶，催化八个电子和八个质子还原二氮和两个质子产生两个等效的氨和一种二氢。电流该酶将N2转化为NH3提出的机制使用了常见的概念许多其他金属辅因子，例如桥接硫化物供体的质子化，使用金属氢化物以存储还原等效物，以及在氢化物和二氮中协调的潜力终端或桥接模式。铁溶血辅因子如何结合氢化物供体和在催化反应过程中，二氮和中间体是基本方面机制，但尚不清楚。这是该提案解决的知识差距。该提议将通过使用底物（Hydrides和Dinitrogen）可以结合的合成簇来实现此目标桥接或终端协调模式，这反映了可能的协调灵活性这些衬底在铁溶血辅助因子上。作为此询问的一部分，该提议将剖析如何桥接配体的数字，身份和连通性调节底物配位。结果该提案中产生的对生化反应具有更广泛的影响，特别是棚屋关于控制多电子多元素氧化还原反应生物催化的原理的启示（例如，光合作用中的水氧化，呼吸减少二氧化物）。

项目成果

期刊论文数量（13）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies.

DOI：
10.1002/ejic.201801404
发表时间：
2019-02
期刊：
European journal of inorganic chemistry
影响因子：
2.3
作者：
Dae Ho Hong;Leslie J. Murray
通讯作者：
Dae Ho Hong;Leslie J. Murray

Dinitrogen Coordination to a High-Spin Diiron(I/II) Species.

DOI：
10.1002/anie.202202329
发表时间：
2022-05-23
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
影响因子：
16.6
作者：
Torres, Juan F.;Oi, Collin H.;Moseley, Ian P.;El-Sakkout, Nabila;Knight, Brian J.;Shearer, Jason;Garcia-Serres, Ricardo;Zadrozny, Joseph M.;Murray, Leslie J.
通讯作者：
Murray, Leslie J.

Isolation of chloride- and hydride-bridged tri-iron and -zinc clusters in a tris(β-oxo-δ-diimine) cyclophane ligand.

在三(β-氧代-β-二亚胺) 环烷配体中分离氯桥和氢化物桥接的三铁和锌簇。

DOI：
10.1039/c9dt00799g
发表时间：
2019
期刊：
Dalton transactions (Cambridge, England : 2003)
影响因子：
0
作者：
Hong,DaeHo;Knight,BrianJ;Catalano,VincentJ;Murray,LeslieJ
通讯作者：
Murray,LeslieJ

Partial Deoxygenative CO Homocoupling by a Diiron Complex.

通过 Diiron 配合物进行部分脱氧 CO 自偶联。

DOI：
10.1002/anie.202308813
发表时间：
2023
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
0
作者：
Singh,Devender;Knight,BrianJ;Catalano,VincentJ;García-Serres,Ricardo;Maurel,Vincent;Mouesca,Jean-Marie;Murray,LeslieJ
通讯作者：
Murray,LeslieJ

Synthetic Factors Governing Access to Tris(β-diketimine) Cyclophanes versus Tripodal Tri-β-aminoenones.

DOI：
10.1021/acs.joc.0c01708
发表时间：
2020-11-06
期刊：
The Journal of organic chemistry
影响因子：
0
作者：
Eaton MC;Knight BJ;Brahmi R;Ferreira RB;Catalano VJ;Rheingold AL;Ghiviriga I;Murray LJ
通讯作者：
Murray LJ