Development of Metal -Sulfur Cluster Molecules Leading to Novel Nitrogen Fixation

金属硫簇分子的开发导致新型固氮

• 批准号: 21350033
• 负责人: SEINO Hidetake
• 金额: $ 12.4万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21350033/
• 关键词: 有機金属化学; 合成化学; 触媒・化学プロセス; 金属-硫黄クラスター; 窒素固定酵素; 水素生成; 小分子活性化; 窒素固定; 金属硫黄クラスター; 無機工業化学

Aiming at the reaction sites for conversion of nitrogen, transition metal-sulfur clusters were investigated as the models for the active site of nitrogenase, which was assembled from multiple metal and sulfur atoms. Stepwise synthetic routes were applied to construct the cluster skeletons, in which four metal and four sulfur atoms were located alternately at the corners of a cube. Reactivity of the cluster that could activate coordinated nitrogen molecule was revealed. Analogous clusters composed of different metal elements were prepared, and specific binding and conversion of hydrazine and carbon monoxide etc. on these clusters were achieved.

针对氮转化的反应位点，研究了由多个金属和硫原子组装而成的过渡金属-硫簇合物作为固氮酶活性位点的模型。采用分步合成的方法构建了四个金属原子和四个硫原子交替排列在立方体四角的簇合物骨架。研究表明，该簇合物具有活化配位氮分子的活性。制备了由不同金属元素组成的类似簇合物，实现了肼、一氧化碳等在这些簇合物上的特异性结合和转化。

项目成果

窒素分子配位キュバン型金属‐硫黄クラスターの反応性とプロトン還元における触媒機能

氮分子配位的古巴金属硫簇的反应活性及其在质子还原中的催化功能

• 发表时间: 2010
• 作者: 清野秀岳;平田恵一;森浩之;溝部裕司
• 通讯作者: 溝部裕司

Incorporation of Fe into the void corner of the incomplete Cubane-type Ir_3S(SH)_3 sulfido-hydrosulfido cluster to give new cubane-type Ir_3FeS_4 clusters

将Fe掺入不完整的古​​巴烷型Ir_3S(SH)_3硫化氢硫簇团簇的空角，得到新的古巴烷型Ir_3FeS_4团簇

• 发表时间: 2010
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Hoda El-Ghamrya;Ken Sakai;Shigeyuki Masaoka;Kamal El-Baradiea;and Raafat Issaa;Takuya Minami;Hidetake Seino
• 通讯作者: Hidetake Seino

Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh_2 and MoIr_2 mixed-metal sulfido clusters

含四膦共配体的Mo双氢硫配合物的制备及其转化为MoRh_2和MoIr_2混合金属硫簇簇

• DOI: 10.1039/b902386k
• 发表时间: 2009
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Kentaro Iwasa;Hidetake Seino;Fumiya Niikura;Yasushi Mizobe
• 通讯作者: Yasushi Mizobe

Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM'Re Cubanes (M = Ir, Rh, Ru; M' = Pt, Pd)

古巴烷型金属硫簇团簇的核心转化反应：MMRe 古巴烷的形状变化、收缩和膨胀（M = Ir、Rh、Ru；M = Pt、Pd）

• DOI: 10.1021/ic100339f
• 发表时间: 2010
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Rie Shibata;Hidetake Seino;Shunpei Fujii;Yasushi Mizobe
• 通讯作者: Yasushi Mizobe

キュバン型RuIr_3S_4クラスターの動的構造変化

古巴型RuIr_3S_4星团的动态结构变化

• 发表时间: 2012
• 作者: M. Yamauchi;Ryu Abe;Tatsuya Tsukuda;清野秀岳
• 通讯作者: 清野秀岳