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.

多金属簇合物由于其邻近金属中心作为独特的有机转化反应位点的适用性而得到广泛研究。我们以前报道过在胺官能团存在下，四核锌簇催化选择性酯交换反应，其选择性与无簇催化剂的反应条件相反。基于四核锌原子簇独特的反应活性，我们将几种多金属原子簇配合物应用于酯转化反应的催化剂。在我们的研究过程中，我们发现，多金属簇和氮基配体的混合物导致形成高活性物种后，配体的簇基序的配位。这种增强效应在锌簇催化的几种酯转化中观察到，此外，八核钴簇在加入2，2 '-联吡啶后成为酯交换的优良催化剂。因此，在催化反应期间通过使用额外配体的这种簇转化是显示高催化性能的一般策略。

项目成果

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

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)

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

End-Functionalized Polymerization of 2-Vinylpyridine through Initial C-H Bond Activation of N-Heteroaromatics and Internal Alkynes by Yttrium Ene-Diamido Complexes

• DOI: 10.1021/ja208293h
• 发表时间: 2011-12-14
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Kaneko, Hiroshi;Nagae, Haruki;Mashima, Kazushi
• 通讯作者: Mashima, Kazushi

Direct Amination of Allylic Alcohols by Amines and Ammonia Catalyzed by Platinium Complexes

铂配合物催化胺和氨直接胺化烯丙醇

• 发表时间: 2011
• 作者: A.Rajendran;S.Nakano;N.Sugimoto;真島和志 他4名
• 通讯作者: 真島和志 他4名