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A Computational Evaluation of the Evidence for the Synthesis of 1,3‐Dimethylcyclobutadiene in the Solid State and Aqueous Solution
Author(s) -
Rzepa Henry S.
Publication year - 2013
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.201102942
Subject(s) - aqueous solution , solid state , state (computer science) , chemistry , materials science , computer science , process engineering , algorithm , engineering
Density functional calculations of 1 H NMR spectra and reaction barriers at the ωB97XD/6‐311G(d,p)/continuum water level do not support the claimed identification of encarcerated 1,3‐dimethylcyclobutadiene in either the solid state or aqueous solution, as reported by Barboiu et al ( Chem. Eur. 2011 , 17 , 10021). Instead, previous suggestions that the species identified in the solid state is in fact 2‐oxabicyclo[2.2.0]hex‐5‐en‐3‐one (the Dewar lactone Me 2 2 ) are reaffirmed. Analysis of the ground‐state electronic structure of this species indicates an unusual π‐anomeric effect is promoting a Dunitz‐like chemical reaction pathway leading to the eventual elimination of carbon dioxide and formation of 1,3‐dimethylcyclobutadiene.