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

• 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
• 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

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：配体对氢化物修饰和还原多铁化合物反应性的影响 抽象的 金属簇辅助因子为底物提供了许多潜在的结合方向，并随后 发生化学变化。对于激活小分子的簇辅助因子尤其如此。 分子底物。该提案的重点是铁钼辅因子的化学 钼依赖性固氮酶，催化八个电子和八个质子还原 氮和两个质子生成两当量的氨和一当量的氢气。目前的 提出的通过该酶将 N2 转化为 NH3 的机制使用了常见的概念 许多其他金属辅助因子，例如桥连硫化物供体的质子化、金属的使用 氢化物储存还原当量，以及协调氢化物和二氮的潜力 终端或桥接模式。铁钼辅助因子如何结合氢化物供体和 二氮以及催化反应过程中的中间体是催化反应的基本方面 机制但仍不清楚。这就是本提案要解决的知识差距。该提案将 通过使用合成簇来实现这一目标，其中底物（氢化物和二氮）可以结合在 桥接或终端协调模式，这反映了协调灵活性 这些底物作用于铁-钼辅因子。作为本次调查的一部分，该提案将剖析如何 桥连配体的数量、特性和连接性调节底物配位。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， 阐明控制多电子多质子氧化还原反应生物催化的原理（例如， 光合作用中的水氧化，呼吸中的双氧还原）。

项目成果

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

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)
• 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)
• 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
• 作者: Eaton MC;Knight BJ;Brahmi R;Ferreira RB;Catalano VJ;Rheingold AL;Ghiviriga I;Murray LJ
• 通讯作者: Murray LJ