Development of Catalytic Reductions with Hydride Complexes in Water

水中氢化物配合物催化还原的进展

• 批准号: 13640568
• 负责人: OGO Seiji
• 金额: $ 2.3万
• 依托单位: Osaka University (2002)Okazaki National Research Institutes (2001)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640568/
• 关键词: Water-soluble Hydride Complexes; Aqua Complexes; Hydrogen Donors; Acid-Catalyzed Reductions; Acidic Media; pH-Dependent; Carbonyl Compounds; Proton; 水中; ヒドリド錯体; 還元; ギ酸イオン; 水素; アクア配位子; 水; 環境; 触媒; 還元反応; 硝酸イオン; X線構造解析

Water-soluble hydride complexes, that were synthesized from the reactions of aqua complexes with hydrogen donors in water, serve as robust and active catalysts for acid-catalyzed reductions of carbonyl compounds in water under acidic conditions. The isolation of the hydride complexes allowed us to investigate robust ability of the hydride complexes in acidic media and reducing ability of the hydride complexes in the reactions with carbonyl compounds under both stoichiometric and catalytic conditions. The rate of the acid-catalyzed reductions are drastically dependent on pH of the solution, reaction temperature, and concentration of the hydrogen donors. The effect of pH on the rate of the reductions is rationalized by the pH-dependent formation of the hydride complexes and activation process of the carbonyl compounds by protons. High turnover frequencies of the acid-catalyzed reductions are ascribed not only to nucleophilicity of the hydride complexes toward the, carbonyl groups activated by protons but also to a protonic character of the hydrido ligands of the hydride complexes that inhibits the protonation of the hydrido ligands.

水溶性氢化物配合物是由水溶性配合物与氢供体在水中反应合成的，其作为在酸性条件下在水中的酸催化还原羰基化合物的稳健且活性的催化剂。氢化物复合物的分离使我们能够研究氢化物复合物在酸性介质中的强大能力以及氢化物复合物在化学计量和催化条件下与羰基化合物反应的还原能力。酸催化还原的速率极大地依赖于溶液的pH、反应温度和氢供体的浓度。pH值对还原速率的影响是合理的pH值依赖的形成的氢化物络合物和活化过程的羰基化合物的质子。高营业额频率的酸催化还原归因于不仅对亲核性的氢化物络合物，由质子活化的羰基，但也到质子的氢化物络合物的配体的质子特性，抑制的配体的质子化的氢化物络合物的的C2H2O配体。

项目成果

Ogo, S. et al.: "pH-Selective Hydrogenation of Water-Soluble Carbonyl Compounds and Alkenes with [Cp^*Ir^<III>(H_2O)_3]^<2+>(Cp^*=η^5-C_5Me_5) as a Catalyst Precursorin Very Acidic Media"Organometallics. 20(3). 497-500 (2001)

Ogo, S. 等人：“使用 [Cp^*Ir^<III>(H_2O)_3]^<2+>(Cp^*=η^5-) 对水溶性羰基化合物和烯烃进行 pH 选择性氢化C_5Me_5)作为强酸性介质中的催化剂前体”有机金属学.20(3).497-500(2001)

Ogo, S. et al.: "pH-Dependent Transfer Hydrogenation, Reductive Amination, and Dehalogenation of Water-Soluble Carbonyl Compounds and Alkyl Halides Promoted by Cp^*IrComplexes"Organometallics. 20(23). 4903-4910 (2001)

Ogo, S. 等人：“Cp^*Ir 配合物促进的水溶性羰基化合物和烷基卤化物的 pH 依赖性转移氢化、还原胺化和脱卤”有机金属化合物。

Ogo, S.et al.: "Structural and Spectroscopic Features of a cis (Hydroxo)-Fe^<III>-(Carboxylato) Configuration as an Active Site Model for Lipoxygenases"Inorganic Chemistry. 41・21. 5513-5520 (2002)

Ogo, S. 等人：“作为脂氧合酶活性位点模型的顺式（羟基）-Fe^<III>-（羧基）构型的结构和光谱特征”无机化学 41・21（2002 年）。 ）

Ogo, S.et al.: "Isolation and Crystal Structure of Water-Soluble Iridium Hydride. Robust and Highly Active Catalyst for Acid-Catalyzed Transfer Hydrogenations of Carbonyl Compounds in Acidic Media"Journal of the American Chemical Society. 125(in press). (

Ogo, S.等人：“水溶性氢化铱的分离和晶体结构。酸性介质中羰基化合物酸催化转移氢化的鲁棒且高活性催化剂”美国化学会杂志。

Ogo, S.et al.: "(Catecholato)iron(III) Complexes : Structural and Functional Models for the Catechol-bound Iron(III) Form of Catechol Dioxygenases"Journal of Inorganic Biochemistry. 88. 284-294 (2002)

Ogo，S.等人：“（儿茶酚）铁（III）复合物：儿茶酚双加氧酶的儿茶酚结合铁（III）形式的结构和功能模型”无机生物化学杂志。