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Chemical fixation and conversion of CO2 into cyclic and cage-type metal carbonates

机译：化学固定并将二氧化碳转化为环状和笼型金属碳酸盐

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Analysis of the Cambridge Structural Database (CSD) revealed over 1200 metal carbonate compounds. At least 130 of them can be described as molecular mono- or polycarbonate metal cage complexes. The formation of most of these structurally diverse compounds is a classic example of serendipitous fixation of atmospheric CO2. Only a small number of compounds of this type were obtained by the intentional addition of Na2CO3, NaHCO3, or other simple carbonates as precursors of carbonate anion. This review article outlines a great potential of CO2 fixation in various inorganic reaction systems as an important pathway to novel entities based on mono- and polycarbonate metal cores. Particularly we focus on: (i) structure and chemistry of carbonate anions and common pathways leading to their generation in inorganic systems, (ii) multinuclear cages with ability to encapsulate CO32- ions, (iii) metal clusters templated by carbonate anions and (iv) carbonate anions as building units of macrocyclic and closed polyhedron systems. This review can be regarded as a flexible guide to the classification of these systems. We present an unusual diversity of molecular structures of metal carbonates derived from the chemical fixation of CO2, and describe composition and geometry of a variety of metal carbonate cores. Unique features of the carbonate anion, i.e. the geometry, low steric hindrance and ability to form a plethora of coordination modes, make it a universal templating agent mediating the formation of a variety of multinuclear aggregates ranging from macrocyclic systems to closed polyhedra. There are also provided some insights into interesting reaction systems, in which the reaction outcome strongly depended on the carbonate's source. The benefits of usage of CO2 as a precursor of carbonate anions are also delineated. When relevant, aspects related to materials chemistry are presented. We believe that the collected results offer a perspective and guidelines for the future research and development of reaction systems leading to metal carbonates of high scientific as well as practical value. (C) 2016 Elsevier B.V. All rights reserved.
机译：剑桥结构数据库（CSD）的分析显示了1200多种金属碳酸盐化合物。它们中的至少130个可以描述为分子单-或聚碳酸酯金属笼络合物。这些结构上大多数不同化合物的形成是大气中二氧化碳偶然固定的一个典型例子。通过有意地添加Na2CO3，NaHCO3或其他简单的碳酸盐作为碳酸盐阴离子的前体，仅获得少量此类化合物。这篇综述文章概述了将CO2固定在各种无机反应系统中的巨大潜力，将其作为通向基于单金属和聚碳酸酯金属核的新型实体的重要途径。我们特别关注以下方面：（i）碳酸根阴离子的结构和化学以及导致它们在无机系统中生成的常见途径，（ii）具有封装CO32-离子能力的多核笼，（iii）由碳酸根阴离子模板化的金属簇，以及（iv ）碳酸根阴离子作为大环和封闭多面体体系的构建单元。该评论可以被视为这些系统分类的灵活指南。我们介绍了从化学固定CO2衍生而来的金属碳酸盐分子结构的异常多样性，并描述了各种金属碳酸盐核的组成和几何形状。碳酸根阴离子的独特特征，即几何形状，低位阻和形成过多配位模的能力，使其成为一种通用模板剂，介导了从大环系统到封闭多面体的多种多核聚集体的形成。还提供了一些有趣的反应系统的见解，其中反应结果强烈取决于碳酸盐的来源。还描述了使用CO 2作为碳酸根阴离子的前体的益处。相关时，介绍与材料化学有关的方面。我们相信，所收集的结果为未来研究和开发导致具有高科学价值和实用价值的金属碳酸盐的反应系统提供了前景和指导方针。 （C）2016 Elsevier B.V.保留所有权利。

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