Why CpAl–Cr(CO)₅ is linear while CpIn–Cr(CO)₅ is not? Understanding the structure and bonding of the CpE–Cr(CO)₅ (E = Group 13 element) complexes

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• 作者：Sukanta Mondal ; Edison Osorio ; Sudip Pan…
• 关键词：Half ; Sandwich ligands ; Coordination compounds ; Bonding analysis
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2016
• 出版时间：October 2016
• 年：2016
• 卷：135
• 期：10
• 全文大小：2,807 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Theoretical and Computational Chemistry
  Inorganic Chemistry
  Organic Chemistry
  Physical Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1432-2234
• 卷排序：135

文摘

Density functional theory computations at the BP86-D3/def2-TZVP level are reported for the CpE–Cr(CO)₅ complexes (E = Group 13 element). In principle, we have answered two important facts: first the nature and trend of the E–Cr bonding along B to Tl complexes; second, the deviation of Cp (centroid)-E–Cr angle in In and Tl from linearity. The bonding situation in the complexes is examined via the natural bond orbital, adaptive natural density partitioning, and energy decomposition analysis schemes. Our results reveal that the E–Cr bonding in the lighter compounds is mainly ionic, while this bonding in the In and Tl complexes is dominated by an orbitalic contribution. We also clarify the origin of deviation of Cp (centroid)-E–Cr angle for the In and Tl complexes using simple molecular orbital arguments and find that the repulsive intermolecular contacts in the crystals are not the real source of this deviation as was claimed.