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Published on: August 13, 2020
The Molecular Structure of gauche-1,3-Butadiene: Experimental Establishment of Non-planarity
Joshua H Baraban1,2, Marie-Aline Martin-Drumel3,4, P Bryan Changala5
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, 80309, USA.
Abstract:
The planarity of the second stable conformer of 1,3-butadiene, the archetypal diene for the Diels-Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level calculations predicted the species to adopt a twisted, gauche structure owing to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the double bonds. The structure cis-1,3-butadiene is unambiguously confirmed experimentally to indeed be gauche with a substantial dihedral angle of 34°, in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche- and trans-butadiene provides an opportunity to examine the effects of conjugation and steric interactions.
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