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The bond length of a carbon−carbon sp2−sp2 σ-bond without the perturbing effects of π-interactions has been estimated by high level calculations on two prototypical systems: a 90°-twisted form of butadiene and the tub conformer of cyclooctatetraene. The former system yields a value of 1.4818 Å, considerably longer than previous estimates. The corresponding bond length in the latter is slightly shorter due to some π-electron delocalization.
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