Crown ether ligation: An approach to low-oxidation-state indium compounds
Crown ether ligation: An approach to low-oxidation-state indium compounds
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DOI：
10.1002/anie.200502901
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Macdonald, CLB
中科院分区：
文献类型：
--
作者：
Andrews, CG;Macdonald, CLB
在过去的20年里，氧化态低于+3的13族元素的化学在主族化学中越来越重要。特别注意力集中在化学的化合物含有13族元素在+1氧化态（EI）的基本和实用的目的。[1-3]EI上的“孤对”电子的存在（方案1a）通常使通常的刘易斯酸性13族中心表现为刘易斯碱。这种改变的反应性意味着含有EI中心的化合物可以用作主族[4]和过渡金属受体的配体;[5，6]由此获得的一些配位络合物已被证明是形成金属间化合物和其他材料的有用前体。[6]尽管空间要求高的取代基如三联苯[7，8]和β-二酮亚胺[9-13]配体已被用于获得一些实例，但绝大多数含有EI中心的稳定单体化合物（除了铊[14]）具有与α（Cp）取代基[15]或等瓣三（吡唑基）硼酸酯基团结合的第13族元素。[16]这些σ-和π-供体取代基稳定
The chemistry of Group 13 elements in oxidation states lower than+ 3 has been a subject of increasing importance in maingroup chemistry over the last 20 years. Particular attention has focused on the chemistry of compounds containing Group 13 elements in the+ 1 oxidation state (EI) for both fundamental and practical purposes.[1–3] The presence of the “lone pair” of electrons on EI (Scheme 1a) often makes the normally Lewis acidic Group 13 center behave as a Lewis base instead. Such altered reactivity means that compounds containing EI centers can be used as ligands for main-group [4] and transition-metal acceptors;[5, 6] some of the coordination complexes thus obtained have proven to be useful precursors for the formation of intermetallic and other materials.[6] Although sterically demanding substituents such as terphenyl [7, 8] and β-diketiminate [9–13] ligands have been used to obtain some examples, the vast majority of stable monomeric compounds containing EI centers (apart from thallium [14]) have the Group 13 element bound to either a cyclopentadienyl (Cp) substituent [15] or to an isolobal tris (pyrazolyl) borate group.[16] These σ-and π-donating substituents stabilize