含有四齿菲咯啉基PNNP配体的铁和钴配合物的金属-配体协同行为。

Metal-ligand cooperation behaviour of Fe and Co complexes bearing a tetradentate phenanthroline-based PNNP ligand.

作者信息

Nakajima Yumiko, Takeshita Tomohiro, Jheng Nai-Yuan

机构信息

Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.

Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577, Japan.

出版信息

Dalton Trans. 2021 Jun 8;50(22):7532-7536. doi: 10.1039/d1dt00476j.

DOI:10.1039/d1dt00476j

PMID:34100488

Abstract

This perspective article describes the synthesis of a series of Fe and Co complexes coordinated with a phenanthroline-based meridional PNNP ligand (2,9-bis((diphenylphosphino)methyl)-1,10-phenanthroline). PNNP-iron(ii) dichloride and -cobalt(i) chloride, [FeCl2(PNNP)] and [CoCl(PNNP)], underwent abstraction of the benzylic H-atom upon treatment with NaOtBu, forming the corresponding deprotonated products [FeCl(PNNP')] (1) and [Co(PNNP')] (2), respectively, each of which bears an asymmetrical PNNP' ligand with a dearomatized phenanthroline backbone as a good metal-ligand cooperation (MLC) scaffold. Complex 2 achieved facile H-H bond cleavage mediated by unique long-range MLC, where the PNNP backbone acts as a H-atom reservoir.

摘要

这篇观点文章描述了一系列与基于菲咯啉的经式PNNP配体（2,9-双（（二苯基膦基）甲基）-1,10-菲咯啉）配位的铁和钴配合物的合成。二氯化PNNP-铁（II）和氯化钴（I），即[FeCl2(PNNP)]和[CoCl(PNNP)]，在用叔丁醇钠处理时发生苄基氢原子的夺取反应，分别形成相应的去质子化产物[FeCl(PNNP')]（1）和[Co(PNNP')]（2），它们各自带有一个具有非芳香化菲咯啉骨架的不对称PNNP'配体，作为良好的金属-配体协同作用（MLC）支架。配合物2通过独特的远程MLC实现了容易的H-H键裂解，其中PNNP骨架充当氢原子储存库。