Love Jason B
EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, The King's Buildings, West Mains Road, Edinburgh, UK EH9 3JJ.
Chem Commun (Camb). 2009 Jun 14(22):3154-65. doi: 10.1039/b904189c. Epub 2009 Apr 27.
Multielectron redox chemistry involving small molecules such as O2, H2O, N2, CO2, and CH4 is intrinsic to the chemical challenges surrounding sustainable, low-carbon energy generation and exploitation. Compounds with more than one metal reaction site facilitate this chemistry by providing both unique binding environments and combined redox equivalents. However, controlling the aggregation of metal cations is problematic, as both the primary coordination spheres of the metals and the metal-metal separations have to be defined carefully. We described recently a series of pyrrole-based macrocyclic ligands designed to manage metal aggregation and form molecular multimetallic complexes. In particular, we have shown that these compartmentalised Schiff-base calixpyrroles generally form rigid Pacman complexes that prescribe well-defined, metallo microenvironments within the molecular cleft. This article will review the development of this chemistry and its context, and will highlight structural facets and reaction chemistry of metal complexes from across the periodic table.
涉及小分子（如O2、H2O、N2、CO2和CH4）的多电子氧化还原化学是围绕可持续、低碳能源生成与利用的化学挑战所固有的。具有多个金属反应位点的化合物通过提供独特的结合环境和组合氧化还原当量来促进这种化学过程。然而，控制金属阳离子的聚集存在问题，因为金属的一级配位球和金属 - 金属间距都必须仔细定义。我们最近描述了一系列旨在控制金属聚集并形成分子多金属配合物的基于吡咯的大环配体。特别是，我们已经表明，这些分隔的席夫碱杯吡咯通常形成刚性的吃豆人配合物，在分子裂隙内规定了明确的金属微环境。本文将综述这种化学的发展及其背景，并突出周期表中各种金属配合物的结构特征和反应化学。
