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

摘要

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 thermolysig of cis,cis- 1,5cyclooctadiene. The three diradical intermediates are connected to the cyclization and dissociation products through conformations that are explored fully here.