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How to Bend a Cumulene
Author(s) -
BarqueraLozada José Enrique
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000025
Subject(s) - cumulene , carbene , bent molecular geometry , chemistry , delocalized electron , computational chemistry , molecule , stereochemistry , organic chemistry , catalysis
Allenes (carbodicarbenes) and [3]cumulenes are linear carbon chains that can be bent when the terminal group has a strong carbene nature. This bending can be quite pronounced in allenes but not in [3]cumulenes. In this study, how N‐heterocyclic or cyclic (alkyl)(amino) carbene (NHC and CAAC, respectively) terminal groups can modify the linear structure of [ n ]cumulenes has been analyzed. A low π acidity of the terminal carbene affects the linearity of [2 n ]cumulenes. Indeed, it has been found 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 over the whole molecule. More significantly, DFT calculations have shown that this bent [4]cumulene is very stable, considerably more so than the corresponding [3]cumulene, which has been elusive to synthesize. Remarkably, calculations have shown that all the NHC [2 n ]cumulenes are more than 25 kcal mol −1 more stable than the [2 n −1]cumulenes.