How to bend a cumulene.

Allenes (carbodicarbenes) and [3]cumulenes are linear carbon chains, which can be bent when the terminal group has a strong carbine nature. This bending can be quite pronounced in allenes but not in [3]cumulenes. We analyse how N-heterocyclic or cyclic (alkyl)-(amino) carbenes (NHC and CAAC, respectively) terminal groups can modify the linear structure of [n]cumulenes. A low π-acidity of the terminal carbene affects the linearity of [2n]cumulenes. We found, indeed, that the NHC [4]cumulene is extremely bent, contrary to classical [4]cumulenes.  The predicted NHC [4]cumulene or tricarbodicarbene has two lone pairs and the π-electrons are delocalized through the whole molecule. More significantly, the DFT calculations show that this bent [4]cumulene is very stable, considerably more than its corresponding [3]cumulene that has been elusive to synthesize. Remarkably, the calculations show that all the NHC [2n]cumulenes are more than 25 kcal/mol more stable than [2n-1]cumulenes.

• Publication year

  2020

• Venue

  Chemistry

• Publication date

  2020-01-25

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/chem.202000025PMID 31981380
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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