Through-bond interactions in the diradical intermediates formed in the rearrangements of bicyclo[n.m.0]alkatetraenes.
The intermediates and transition structures in the degenerate thermal rearrangements of bicyclo[4.4.0]deca-2,4,7,9-tetraene (1c), bicyclo[5.5.0]dodeca-2,4,8,10-tetraene (11b), and bicyclo[5.4.0]undeca-2,4,8,10-tetraene (14) have been located by (U)B3LYP/6-31G(d) calculations. The singlet-triplet energy differences (ΔE(ST)) in the diradical intermediates (tricyclo[4.4.0.0(2,7)]deca-3,8-dien-5,10-diyl (2c), tricyclo[5.5.0.0(5,11)]dodeca-2,8-dien-4,10-diyl (12b), and tricyclo[5.4.0.0(5,11)]undeca-2,8-dien-4,10-diyl (15)) have been computed, using both UB3LYP and (6/6)CASPT2 calculations. ΔE(ST) in 2c, in which a four-membered ring is anti-bridged by two allylic radicals, is computed to be larger by a factor of 5 than ΔE(ST) in 15, in which the anti-bridged ring is five-membered, and by a factor of 10 than that in 12b, in which the anti-bridged ring is six-membered. The reasons for the much larger interaction between two allylic radicals through the bonds of the four-membered ring in 2c than through the bonds of the five-membered ring in 15 or the six-membered ring in 12b are discussed, and the consequences of the large, through-bond stabilization of the singlet state of 2c are described.
Lovitt
Charity Flener
CF
Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle No. 305070, Denton, Texas 76203-5017, USA.
Dong
Hao
H
Hrovat
David A
DA
Gleiter
Rolf
R
Borden
Weston Thatcher
WT