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.
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.
Caramella
Pierluigi
P
Dipartimento di Chimica Organica, Università degli Studi di Pavia, Viale Taramelli 10, 27100 Pavia, Italy. pierluigi.caramella@unipv.it
Quadrelli
Paolo
P
Toma
Lucio
L
Romano
Silvano
S
Khuong
Kelli S
KS
Northrop
Brian
B
Houk
K N
KN