AbstractDensity functional calculations of 1H 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 Me22) 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.

AbstractFollowing earlier reports on the photochemical synthesis of 1,3‐dimethylcyclobutadiene8, 10 in a protective host matrix, theoretical calculations for the formation of that adduct have been recently performed by Rzepa.13 The author formulated criticisms based mainly on density functional theory calculations of 1H NMR spectra. According to Rzepa the calculated spectra do not correspond with our measured spectra, which leads him to the conclusion that our interpretation is wrong, and that mainly cyclobutadiene has not been stabilized or even synthesized; we believe, however, that the initial model that Rzepa used for his calculations does not correspond to chemical reality or is at the very least a crude simplification of it, which implies that his calculations cannot match, in every point, our experimental spectra. Rzepa′s simplified models might be ‘reasonable’ from the theoretical point of view; however, in the case of assessment in the solid state, the theoretical setup does not force the system to preserve the confined stabilizing space defined by the crystalline matrix for encapsulated hosts in the solid state. Inversely, in the case of solution modeling, the theoretical setup is too rigid to properly assess the complex equilibria occurring in solution and to accurately determine the NMR spectra of exchanging species in solution. The inconsistency between our experimental results and the results of the theoretical models proposed by Rzepa is such that his conclusions are considered to be too far from experimental reality. Accurate modeling taking in account “reasonable” experimental details would be a worthwhile endeavor.

Snapshot of a Strained Ring Benzene and cyclobutadiene possess diametrically opposed properties. The former, a hexagonal hydrocarbon with a geometry perfectly suited to its bonding arrangement, exhibits unusual stability. The latter, with its two fewer carbons tightly squeezed into the right angles of a 4-membered ring, rapidly forms a dimer to relieve its considerable geometric and electronic strain. Monomeric cyclobutadiene was first isolated in substantial quantity by confining it within a molecular shell, but it has eluded full structural characterization. Legrand et al. (p. 299 ) have now found a host lattice that stabilizes a dimethyl-substituted derivative of the molecule sufficiently to allow analysis of its structure and bonding motif by x-ray diffraction.