Sigma Bonds as Ligand Donor Groups in Transition Metal Complexes

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• 关键词：Agostic complex ; Dihydrogen complex ; Sigma complex
• 刊名：Structure & Bonding
• 出版年：2017
• 出版时间：2017
• 年：2017
• 卷：171
• 期：1
• 页码：63-77
• 全文大小：285 KB
• 参考文献：1.Crabtree RH (2013) The organometallic chemistry of the transition metals. Wiley-VCH, Hoboken
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• 作者单位：Robert H. Crabtree (3)
  
  3. Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, 06520-8107, 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

Covalent X–H bonds, particularly where X is H, C, B, and Si, can act as Lewis base ligands in forming metal complexes of general type L _n M(H–X), where the M–H–X angle is strongly bent so that the coordination can best be considered as side-on. The binding is greatly enhanced by back donation from the metal into the X–H σ* orbital. This elongates and eventually breaks the X–H bond, leading to characteristic structural, physicochemical characteristics and alteration of the reactivity of the ligand. The requirement for back donation means that the appropriate L _n M fragment must usually have appreciable π donor character. Since the binding of the X–H bond to the metal center is relatively weak, and the binding of the deprotonated X− group left behind is much stronger, the binding also facilitates proton loss from the X–H bond. This electron redistribution results in reactivity differences which may be exploited. The case of H₂ is treated in most detail in this review, because of its central place in the field.