N-Heterocyclic Carbene-Functionalized Gold Nanoclusters

N-杂环卡宾功能化金纳米团簇

• 批准号: 19F19741
• 负责人: CRUDDEN Cathleen
• 金额: $ 0.77万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2019
• 资助国家: 日本
• 起止时间: 2019-07-24 至 2020-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19F19741/
• 关键词: Nano Materials; Nanocluster; N-Heterocyclic Carbene; Gold

More recently, we have been working to expand the use of NHCs to the stabilization of gold nanoclusters. Following our initial report on the synthesis and isolation of [Au13(NHC)9Cl3]Cl2 clusters, we improved the isolation and purification procedures further in order to apply these clusters as catalysts in various reactions.And structures of clusters was confirmed by X-ray crystallographic analysis. After developing optimized procedures for the synthesis and purification of these clusters, we sought to test their activity in oxidation catalysis, along with our previously isolated NHC-phosphine ligated clusters. Towards this end we chose two model reactions, benzyl alcohol oxidation and photocatalytic benzyl amine oxidation as test cases. Benzyl alcohol oxidation using mixed phosphine/NHC Au13 clusters proceeds with moderate turnover frequency (average 7 h-1), producing benzaldehyde with high selectivity (average 95%). Due to the low stability of these clusters under catalytic conditions, we are currently investigating increasing their stability via solid supports and/or ligand modifications. We plan to also investigate other novel catalytic reactions using our family of NHC-functionalized gold nanoclusters in future research.

最近，我们一直致力于将 NHC 的用途扩大到金纳米团簇的稳定化。继我们对[Au13(NHC)9Cl3]Cl2团簇的合成和分离的初步报告之后，我们进一步改进了分离和纯化程序，以便将这些团簇作为催化剂应用于各种反应中。并通过X射线证实了团簇的结构晶体学分析。在开发了这些簇的合成和纯化的优化程序后，我们试图测试它们的氧化催化活性，以及​​我们之前分离的 NHC-膦连接簇。为此，我们选择了两个模型反应：苯甲醇氧化和光催化苯甲胺氧化作为测试用例。使用混合膦/NHC Au13 簇进行苯甲醇氧化，周转频率适中（平均 7 h-1），产生高选择性（平均 95%）的苯甲醛。由于这些簇在催化条件下的稳定性较低，我们目前正在研究通过固体支持物和/或配体修饰来提高它们的稳定性。我们还计划在未来的研究中使用我们的 NHC 功能化金纳米团簇家族来研究其他新颖的催化反应。

项目成果

クイーンズ大学(カナダ)

女王大学（加拿大）

ユバスキュラ大学(フィンランド)

于韦斯屈莱大学（芬兰）

N-heterocyclic carbene-functionalized magic-number gold nanoclusters

• DOI: 10.1038/s41557-019-0246-5
• 发表时间: 2019-05-01
• 期刊: NATURE CHEMISTRY
• 影响因子: 21.8
• 作者: Narouz, Mina R.;Osten, Kimberly M.;Crudden, Cathleen M.
• 通讯作者: Crudden, Cathleen M.