Construction of tetrahedral chiral-at-metal complexes towards asymmetric light-driven redox catalysis

构建四面体手性金属配合物以实现不对称光驱动氧化还原催化

基本信息

批准号：
22KJ0852
负责人：
LIU Yuanfei
金额：
$ 1.09万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for JSPS Fellows
财政年份：
2023
资助国家：
日本
起止时间：
2023-03-08 至 2024-03-31
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-22KJ0852/
关键词：
nickel cobalt chiral-at-metal tetrahedral geometry redox-active spontaneous resolution

项目摘要

In one year research, I mainly focus on construction and resolution of redox-active chiral-at-nickel(II) and chiral-at-cobalt(II) complexes.First, I constructed two tetrahedral chiral-at-nickel(II) complexes using an unsymmetrical, achiral tridentate ligand and characterized them by NMR, ESI-MS, single-crystal XRD and UV-vis absorption spectroscopy. The structural information was carefully elucidated. The complexes adopt a tetrahedral geometry and exhibit redox activity as well as visible-light absorption. Also, they are capable of ligand exchange for substrate activation.Second, I succeeded in spontaneous resolution of S/R-[NiL(ClLi(thf)2)] complex to conglomerate crystals at low temperature. I optimized the crystallization conditions and elucidated the crystallographic structure. I found that hydrogen bondings are essential to achieve spontaneous resolution. Starting from achiral building blocks, the ligands and nickel ions assemble chiral-at-metal complexes, 1D chiral helices, 3D chiral suprastructure and finally homochiral crystals in a highly asymmetric manner. This is related to the origin of homochirality in biological systems in ancient earth and sheds light on the concept of crystal engineering.I also successfully constructed a tetrahedral chiral-at-cobalt(II) complex and charactered it by NMR, ESI-MS, single-crystal XRD, UV-vis absorption spectroscopy. Together with silver salts, the complex was found to be capable for carbon-carbon bond cleavage of 1,2-diarylethylenediamine. The reaction condition is under optimization currently.

在一年的研究中，我主要专注于建造和解决氧化还原活跃的手性nickel（ii）和手性 - 贝果（II）络合物。首先，我使用一个不太成熟的，可观的，可观的，酸痛的trige trigatate ligand and nms-nms nms，ubs ubs，ubs，nms，ubs，nms，sims，nms，x-sms，ubs，un-sms，x-sms sms，x-sms，nms，吸收光谱。仔细阐明了结构信息。这些复合物采用四面体几何形状，表现出氧化还原活性以及可见光的吸收。同样，它们能够配体交换底物激活。第二，我成功地分辨出了s/r- [nil（clli（thf）2）]在低温下晶体的复合物。我优化了结晶条件并阐明了晶体学结构。我发现氢键对于实现自发分辨率至关重要。从ACHIRAL构建块开始，配体和镍离子在金属配合物中组装了手性，1D手性螺旋，3D手性超构造以及最终以高度不对称的方式组装同型晶体。这与古代地球生物系统中的同质病的起源有关，并阐明了晶体工程的概念。我还成功构建了四面体手性含量（II）复合物（II）复合物，并由NMR，ESI-MS，单晶体，单晶体XRD，UV-Vis-Vis吸收光谱镜进行表征。与银盐一起，发现该络合物能够用于1,2-二甲基二胺的碳碳键裂解。反应条件目前处于优化状态。