Reductive coupling of carbon monoxide to glycolaldehyde and hydroxypyruvaldehyde polyanions in binuclear cyclopentadienyl lanthanum and lutetium derivatives: analogies to cyclooctatetraene thorium chemistry

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• 作者：Huidong Li ; Hao Feng ; Weiguo Sun ; Qunchao Fan…
• 关键词：Carbon monoxide coupling ; Lanthanides ; Lutetium ; Lanthanum ; Cyclopentadienylmetal derivatives ; Reductive coupling ; Glycolaldehyde ; Hydroxypyruvaldehyde ; Density functional theory
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2016
• 出版时间：January 2016
• 年：2016
• 卷：135
• 期：1
• 全文大小：859 KB
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• 作者单位：Huidong Li (1)
  Hao Feng (1)
  Weiguo Sun (1)
  Qunchao Fan (1)
  R. Bruce King (2)
  Henry F. Schaefer III (2)
  Yinxue Liu (1)
  
  1. Research Center for Advanced Computation, School of Science, Xihua University, Chengdu, 610039, China
  2. Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA, 30602, USA
  
• 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

文摘

Cloke and coworkers have recently (2006–2012) shown that reaction of carbon monoxide with organouranium compounds results in reductive coupling to yield the oligomeric anions C _n O _n 2− (n = 2, 3, 4). In order to explore the possibilities of similar reductive coupling of carbon monoxide in organolanthanide systems, the structures and thermochemistry of the cyclopentadienyllanthanide carbonyls Cp₂Ln₂(CO) _n (n = 2, 3, 4, 5) have been investigated using lanthanum and lutetium, which are diamagnetic in the favored +3 oxidation state. All of these Cp₂Ln₂(CO) _n structures have long Ln···Ln distances exceeding 4.2 Å for La and 3.6 Å for Lu, indicating the lack of direct metal–metal bonding and suggesting the normally favored +3 oxidation state for these lanthanides. In the dicarbonyls Cp₂Ln₂(CO)₂, the two CO groups couple to form a bridging µ-C₂O₂ 4− ligand, which can be derived by removal of four protons from glycolaldehyde (hydroxyacetaldehyde). Similarly, in the tricarbonyls, the three CO groups couple to form a bridging µ-C₃O₃ 4− ligand, which can be derived by removal of four protons from hydroxypyruvaldehyde. However, the lowest energy structures for the tetracarbonyls Cp₂Ln₂(CO)₄ (by more than 13 kcal/mol) have four separate η2-µ-CO ligands bonded to the central Ln₂ unit through both their carbon and oxygen atoms. Thermochemistry of the Cp₂Ln₂(CO) _n systems suggests viability of Cp₂Ln₂(CO)₂ and Cp₂Ln₂(CO)₄. However, Cp₂Ln₂(CO)₃ is predicted to be disfavored relative to disproportionation into Cp₂Ln₂(CO)₂ + Cp₂Ln₂(CO)₄.