Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters

被引：17

作者：

Cadenbach, Thomas ^{[1
]}

Pankhurst, James R. ^{[1
]}

Hofmann, Tommy A. ^{[2
]}

Curcio, Massimiliano ^{[1
]}

Arnold, Polly L. ^{[1
]}

Love, Jason B. ^{[1
]}

机构：

[1] Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3FJ, Midlothian, Scotland

[2] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 11期

基金：

英国工程与自然科学研究理事会;

关键词：

OXYGEN-EVOLVING COMPLEX; PHOTOSYSTEM-II; SMALL MOLECULES; METAL; REDUCTION; LIGAND; COORDINATION; SILYLATION; ACTIVATION; CHEMISTRY;

D O I：

10.1021/om501244n

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The design of ligands that can act as platforms for the controlled; "bottom-up" synthesis of transition-metal clusters is a promising approach to accessing enzymatic mimics and new small-molecule reaction chemistry. This approach is exemplified here through the coordination chemistry of two compartmental Schiff-base calixpyrroles (H4L) that usually act as dinucleating ligands for transition metals. While reactions between H4L and Zn{N(SiMe3)(2)}(2) form the expected dinuclear Zn "Pacman" complexes Zn-2(L), reactions with ZnEt2 result in the tetranuclear Zn alkyl complexes Zn4Et4(THF)(4)(L), in which open, "bowl-shaped" structures are adopted due to the flexibility of the macrocyclic platform: The outcome of hydrolysis reactions of these tetranuclear complexes is found to depend on the macrocyclic Cavity size, with the smaller macrocycle favoring oxo formation in Zn-4(mu(4)-O)Et-2(L) and the larger macrocycle favoring complete hydrolysis to form the hydroxide-bridged cluster Zn-4(mu(2)-OH)(4)(L). This latter complex reacts with carbon dioxide at elevated temperature, reforming the free macrocycle H4L and eliminating ZnCO3.

引用

页码：2608 / 2613

页数：6

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