Synthesis of Coordinatively Unsaturated Iron Complexes and C-H Bond Activation

配位不饱和铁配合物的合成及C-H键活化

• 批准号: 20613004
• 负责人: OHKI Yasuhiro
• 金额: $ 2.83万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20613004/
• 关键词: 鉄; C-H結合活性化; 配位不飽和; 有機金属; 触媒; 有機金属錯体; N-ヘテロ環カルベン

The activation of C-H bonds is a key elementary step of organometallic reactions, and has great utility in organic synthesis. As a requirement for successful C-H bond activation under mild conditions would be preparation of coordinatively unsaturated complexes, we have synthesized coordinatively unsaturated half-sandwich iron complexes of N-heterocyclic carbenes. The sequential C-H bond activation and borylation reactions were found to occur upon treatment of the iron complexes with thiophene, furan, benzothiophene, benzofuran, or pyridine, followed by addition of hydroboranes. Based on these findings on stoichiometric reactions, we have developed the catalytic C-H bond activation/borylation of furans and thiophenes mediated by a half-sandwich iron complex of the methyl-substituted N-heterocyclic carbene. We have also conducted a series of reactions of the new iron complexes with nearly stoichiometric amount of substrate, to gain mechanistic insights.

C-H键的活化是有机金属反应的关键基本步骤，在有机合成中具有重要的用途。由于在温和条件下成功活化C-H键的必要条件是制备配位不饱和配合物，我们合成了N-杂环卡宾配位不饱和半夹心铁配合物。发现用噻吩、呋喃、苯并噻吩、苯并呋喃或吡啶处理铁络合物，然后添加氢硼烷，会发生连续的 C-H 键活化和硼化反应。基于这些化学计量反应的发现，我们开发了由甲基取代的N-杂环卡宾的半夹心铁络合物介导的呋喃和噻吩的催化C-H键活化/硼基化。我们还对新型铁配合物与接近化学计量的底物进行了一系列反应，以获得机理见解。

项目成果

An Iron(II) Carbonyl Thiolato Complex Bearing 2-Methoxy-Pyridine : A Structural Model of the Active Site of [Fe] Hydrogenase

带有 2-甲氧基-吡啶的铁(II)羰基硫代络合物：[Fe]氢化酶活性位点的结构模型

• 发表时间: 2010
• 作者: Soichiro Tanino; Yasuhiro Ohki; Kazuyuki Tatsui
• 通讯作者: Kazuyuki Tatsui

A Dithiolate-Bridged (CN)2(CO)Fe-Ni Complex Reproducing the IR Bands of [NiFe] Hydrogenase

二硫醇桥 (CN)2(CO)Fe-Ni 配合物再现 [NiFe] 氢化酶的红外光谱带

• 发表时间: 2009
• 作者: Soichiro Tanino; Zilong Li; Yasuhiro Ohki; Kazuyuki Tatsumi
• 通讯作者: Kazuyuki Tatsumi

C-H Bond Activation of Heteroarenes Mediated by a Half-Sandwich Iron Complex of N-Heterocyclic Carbene

N-杂环卡宾半夹心铁配合物介导的杂芳烃C-H键活化

• 发表时间: 2008
• 作者: Yasuhiro Ohki; Tsubasa Hatanaka; Kazuyuki Tatsumi
• 通讯作者: Kazuyuki Tatsumi

Reductive Fusion of Two [Fe_4S_4] Clusters into an [Fe_8S_7] Core of Nitrogenase P-Cluster

两个 [Fe_4S_4] 簇还原融合成固氮酶 P 簇的 [Fe_8S_7] 核心

• 发表时间: 2010
• 作者: Y.Ohki; N.Yamada; K.Tanifuji; K.Tatsumi
• 通讯作者: K.Tatsumi

錯体化学選書 超分子錯体の化学

配位化学选择：超分子配合物的化学

• 发表时间: 2009
• 作者: 大木靖弘; 巽和行
• 通讯作者: 巽和行