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

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 compartm...

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Autor Principal: Cadenbach, Spyros Thomas
Formato: Artículos
Lenguaje:eng
Publicado: 2016
Materias:
MACROCYCLIC
TETRANUCLEAR
OXO AND HYDROXO
ZINC CLUSTERS
Acceso en línea:http://repositorio.educacionsuperior.gob.ec/handle/28000/3404
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spelling oai:localhost:28000-34042017-04-11T22:16:47Z Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters Cadenbach, Spyros Thomas MACROCYCLIC TETRANUCLEAR OXO AND HYDROXO ZINC CLUSTERS 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 Zn2(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 Zn4(?4-O)Et2(L) and the larger macrocycle favoring complete hydrolysis to form the hydroxide-bridged cluster Zn4(?2-OH)4(L). This latter complex reacts with carbon dioxide at elevated temperature, re-forming the free macrocycle H4L and eliminating ZnCO3. Escuela Polit?cnica Nacional http://pubs.acs.org/doi/abs/10.1021/om501244n 2016-11-10T16:42:57Z 2016-11-10T16:42:57Z 2015 article Cadenbach, Spyros Thomas. et al.(2016). Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters. Organometallics. Vol.34, N?11. pp. 2608-2613 0276-7333 http://repositorio.educacionsuperior.gob.ec/handle/28000/3404 eng restrictedAccess pp. 2608-2613
institution SENESCYT
collection Repositorio SENESCYT
biblioteca Biblioteca Senescyt
language eng
format Artículos
topic MACROCYCLIC
TETRANUCLEAR
OXO AND HYDROXO
ZINC CLUSTERS
spellingShingle MACROCYCLIC
TETRANUCLEAR
OXO AND HYDROXO
ZINC CLUSTERS
Cadenbach, Spyros Thomas
Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
description 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 Zn2(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 Zn4(?4-O)Et2(L) and the larger macrocycle favoring complete hydrolysis to form the hydroxide-bridged cluster Zn4(?2-OH)4(L). This latter complex reacts with carbon dioxide at elevated temperature, re-forming the free macrocycle H4L and eliminating ZnCO3.
author Cadenbach, Spyros Thomas
author_facet Cadenbach, Spyros Thomas
author_sort Cadenbach, Spyros Thomas
title Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
title_short Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
title_full Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
title_fullStr Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
title_full_unstemmed Macrocyclic Platforms for the Construction of Tetranuclear Oxo and Hydroxo Zinc Clusters
title_sort macrocyclic platforms for the construction of tetranuclear oxo and hydroxo zinc clusters
publishDate 2016
url http://repositorio.educacionsuperior.gob.ec/handle/28000/3404
_version_ 1634995140622811136
score 11,871979

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