Non‐covalent Stabilization in Transition Metal Coordination and Organometallic Complexes
Non‐covalent Stabilization in Transition Metal Coordination and Organometallic Complexes
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DOI：
10.1002/9781119113874.ch7
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发表时间：
2016-05
期刊：
影响因子：
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通讯作者：
P. Petrović;J. Djukic;A. Hansen;Christoph Bannwarth;S. Grimme
中科院分区：
文献类型：
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作者：
P. Petrović;J. Djukic;A. Hansen;Christoph Bannwarth;S. Grimme
非共价相互作用（NCI）在自然界中无处不在，它们在过渡金属化学中的作用的演示仍然是一个生动的研究领域。事实上，更好地理解NCIs与共价相互作用的相互作用仍然是至关重要的，因为它可以为新的功能性有机金属配合物的工程设计的新的概念框架的基础。本章讨论了从头算量子化学研究的挑战，特别是在其贡献的有机金属系统与其固有的复杂性建模。最近开发的方法可以将NCIs的贡献纳入化学键和其他键合关系的分析中。新的方法开发，以产生一个更准确的评价涉及过渡金属络合物在溶液中的反应的热化学的观点和分析。NCIs的分子内稳定作用也审查了特殊情况下的双金属嵌段过渡金属配合物的挑战，通过其结构特征，经验朗缪尔-西季威克18电子规则。文献数据库的处理以时间顺序的方式呈现，以概述多年来在处理金属-金属相互作用方面的实践变化，从基于静态晶体X射线衍射分析产生的结构信息的演绎方法到考虑固有分子动力学的全面理解键合。进一步回顾了NCI在基于过渡金属的供体-受体络合物和在溶液中显示出显著持久性的过渡金属络合物的其他聚集体的特殊情况下的分子间稳定作用。
Non‐covalent interactions (NCIs) are ubiquitous in nature, and the demonstration of their role in transition metal chemistry remains a vivid domain of research. Indeed, a better understanding of the interplay of NCIs with covalent interactions remains critical as it may create the basis for new conceptual frameworks for the engineering of new functional organometallic complexes. This chapter deals with the challenges of the research inab initioquantum chemistry particularly in its contribution to the modeling of organometallic systems with their inherent complexity. Including the contribution of NCIs into the analysis of chemical bonds and other bonding relationships is at reach with recently developed methods. Views and analyses of novel methodologies developed to produce a more accurate evaluation of the thermochemistry of reactions involving transition metal complexes in solution are presented. The intramolecular stabilizing role of NCIs is also reviewed for particular cases of bimetallicd‐block transition metal complexes that challenge, by their structural features, the empirical Langmuir–Sidgwick 18 electron rule. The treatment of the literature corpus of data is presented in a chronological fashion to outline the changes of practice over the years in the treatment of metal–metal interactions from a deductionist approach based on structural informations produced by static crystal X‐ray diffraction analyses toward a comprehensive apprehension of bonding taking into consideration inherent molecular dynamics. Further review of intermolecular stabilizing effects of NCIs in peculiar cases of transition metal‐based donor–acceptor complexes and other aggregates of transition metal complexes that display remarkable persistence in solution is presented.