The Covalent Bond Classification Method and Its Application to Compounds That Feature 3-Center 2-Electron Bonds

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• 关键词：Agostic interaction ; Bridging alkyl ; Bridging carbonyl ; Bridging hydride ; 3c–2e interaction ; σ ; Complex
• 刊名：Structure & Bonding
• 出版年：2017
• 出版时间：2017
• 年：2017
• 卷：171
• 期：1
• 页码：79-139
• 全文大小：1,493 KB
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• 作者单位：Malcolm L. H. Green (3)
  Gerard Parkin (4)
  
  3. Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK
  4. Department of Chemistry, Columbia University, New York, NY, 10027, USA
  
• 丛书名：The Chemical Bond III
• ISBN：978-3-319-35146-9
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1616-8550
• 卷排序：171

文摘

This article provides a means to classify and represent compounds that feature 3-center 2-electron (3c–2e) interactions according to whether (1) the two electrons are provided by one or by two atoms; (2) the central bridging atom provides two, one, or zero electrons; and (3) the interaction is open or closed. Class I 3c–2e bonds are defined as those in which two atoms each contribute one electron to the 3-center orbital, while Class II 3c–2e bonds are defined as systems in which the pair of electrons are provided by a single atom. The use of appropriate structure-bonding representations enables the [ML _l X _x Z _z ] covalent bond classification of the element of interest to be evaluated. This approach is of considerable benefit in predicting metal–metal bond orders that are in accord with theory for dimetallic compounds that feature bridging hydride and carbonyl ligands.