Multimetallic cluster complexes as well-defined nano-scale catalysts for novel organic transformations

多金属簇配合物作为新型有机转化的明确纳米级催化剂

• 批准号: 21245027
• 负责人: MASHIMA Kazushi
• 金额: $ 31.03万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 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/en/grant/KAKENHI-PROJECT-21245027/
• 关键词: クラスター; ナノ触媒; 触媒反応; ナノ反応場; 多核金属錯体; アミド; エステル; エタノールアミド; アミド分解反応; 亜鉛触媒; 多核触媒; クラスター触媒; ナノ構造触媒; 官能基変換反応; 末端官能基化; メタラサイクル錯体; 炭素-水素結合活性化; C-H結合活性化; 環化反応; ハフニウム錯体; メタラサイクル; カチオン性錯体; 2+2+1環化付加反応; 内部アセチレン; 亜鉛; コバルト; 4核錯体; エステル交換反応; 官能基

Multimetallic cluster complexes have been extensively studied due to their applicability of proximal metal centers as a reactive site for unique organic transformations. We previously reported a tetranuclear zinc cluster catalyzed selective trans-esterification in the presence of amine functionalities, and the selectivity was opposite trend to the cluster catalyst free reaction condition. Based on the unique reactivity of the tetranuclear zinc cluster, we applied several multimetallic cluster complexes as catalysts for ester transformations. During our research, we found that the mixture of multimetallic clusters and nitrogen-based ligands led to the formation of highly reactive species after the coordination of the ligands to the cluster motif. Such enhancement effects were observed in zinc cluster catalyzed several ester transformations, and in addition, octanuclear cobalt clusters became an excellent catalyst for trans-esterification upon addition of 2,2’-bipyridine. Therefore, such cluster transformation during the catalytic reaction by using additional ligands is general strategy for showing high catalytic performance.

由于将近端金属中心用作独特的有机转化的反应位点，因此多金属簇复合物已被广泛研究。我们先前报道了在存在胺功能的情况下催化了四核锌簇催化选择性的跨酯化，并且选择性与簇催化剂自由反应条件相反。基于四核锌簇的独特反应性，我们将几种多金属簇复合物应用于酯转换的催化剂。在我们的研究过程中，我们发现多金属簇和基于氮的配体的混合物导致配体协调与簇基序的配位后形成了高反应性物种。在催化几种酯转化的锌簇中观察到了这种增强作用，此外，添加了2,2'Bipyridine后，八核钴簇成为跨酯化的极好催化剂。因此，通过使用其他配体在催化反应过程中这种簇转化是表现出高催化性能的一般策略。

项目成果

コバルト触媒を用いた水酸基選択的アシル化反応の反応機構

钴催化剂羟基选择性酰化反应的反应机理

• 作者: Y.Zhang;T.Motohashi;Y.Masubuchi;S.Kikkawa;林結希子・大嶋孝志・真島和志
• 通讯作者: 林結希子・大嶋孝志・真島和志

Platinum-Catalyzed Direct Amination of Allylic Alcohols under Mild Conditions

温和条件下铂催化烯丙醇的直接胺化

• 发表时间: 2009
• 作者: T.Ohshima;K.Mashima;(他4名)
• 通讯作者: (他4名)

A Simple, General, and Highly Chemoselective Acetylation of Alcohols Using Ethyl Acetate as the Acetyl Donor Catalyzed by a Tetranuclear Zinc Cluster

• DOI: 10.1055/s-0029-1217335
• 发表时间: 2009-06-17
• 期刊: SYNLETT
• 影响因子: 2
• 作者: Iwasaki, Takanori;Maegawa, Yusuke;Mashima, Kazushi
• 通讯作者: Mashima, Kazushi

Efficient cyclic carbonate synthesis catalyzed by zinc cluster systems under mild conditions

• DOI: 10.1039/c1cy00404b
• 发表时间: 2012-03
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Yi Yang;Y. Hayashi;Y. Fujii;Takuto Nagano;Yusuke Kita;T. Ohshima;J. Okuda;K. Mashima

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