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The Three Corrugated Surfaces of 1,4-Divinyltetramethylene Diradical Intermediates and Their Connections to 1,2-Divinylcyclobutane, 4-Vinylcyclohexene, 1,5-Cyclooctadiene, and Two Butadienes

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journal contribution
posted on 15.04.2005, 00:00 by Pierluigi Caramella, Paolo Quadrelli, Lucio Toma, Silvano Romano, Kelli S. Khuong, Brian Northrop, K. N. Houk
The three potential energy surfaces of the trans-trans, cis-trans, and cis-cis divinyltetramethylene diradicals have been located with DFT calculations at the BPW91/6-311+G** levels. The three surfaces account well for the experimental results reported for the thermolysis of optically active trans-1,2-divinylcyclobutane and optically active and deuterated 4-vinylcyclohexene. The surfaces account also for the outcome of the dimerization of butadiene and the thermolysis of cis,cis-1,5-cyclooctadiene. The three diradical intermediates are connected to the cyclization and dissociation products through conformations that are explored fully here.