Spontaneous Formation of a Doubly Interlocking [2] Catenane Using Copper (I) and Palladium (II) as Templating and Assembling Centers

使用铜 (I) 和钯 (II) 作为模板和组装中心自发形成双联锁 [2] 链烷

基本信息

批准号：
10044104
负责人：
FUJITA Makoto
金额：
$ 2.24万
依托单位：
Nagoya University (1999)Okazaki National Research Institutes (1998)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10044104/
关键词：
Self-assembly Catenane Template Palladium ESI-MS Phenanthroline 内部連結構造キラリティー電気化学

项目摘要

Doubly interlocking catenanes are chiral and complex topologies which have only been described recently. Our approach is to combine the two methods, based on coordination chemistry, which are termed as "template" and "self-assembly" strategies. In the template strategy, copper(I) complexes have been used as precursors, affording simple to topologically very complex catenanes.On the other hand, the self-assembly process furnishes in one chemical step sophisticated structures, including interlocking rings, from very simple molecular fragments and under mild conditions. A new method based on these two strategies has been used to construct a 4-crossing [2]catenane. The ligand used contains a central 1, 10-phenanthroline site attached to two pendent/4-pyridyl groups. The central site is used to complex a copper(I) center whereas the lateral pyridine groups are coordinated to palladium(II). The stepwise complexation procedure is virtually quantitative. It can be carried out both ways (copper(I) followed by palladium(II) or reverse) : The final complex is a chiral species incorporating 4 ligands, 2 copper(I) and 4 palladium(II) centers. It has been characterized in solution and its structure has been evidenced by ESI-MS.

双重互锁的Catenanes是手性且复杂的拓扑结构，直到最近才描述。我们的方法是基于协调化学的两种方法，称为“模板”和“自组装”策略。在模板策略中，铜（i）络合物已被用作前体，提供了简单的拓扑学上非常复杂的蛋糕。另一方面，自组装过程在一个化学步骤的复杂结构中提供了一个化学步骤的复杂结构，包括互锁环，来自非常简单的分子片段，在温和的条件下。一种基于这两种策略的新方法已用于构建4横烷[2] Catenane。使用的配体包含一个附着在两个吊坠/4-吡啶基组的中央1个，10-苯磺胺位点。中央部位用于复杂铜中心（i）中心，而吡啶侧吡啶组则配位为钯（II）。逐步络合过程实际上是定量的。它可以两种方式进行（铜（i），然后是钯（II）或反向）：最终的配合物是一种手性物种，其中包含4种配体，2个铜（I）和4个钯（II）中心。它已经在溶液中表征，其结构已通过ESI-MS证明。