Complete Structure of trans-3,4-Difluorocyclobutene from Microwave Spectroscopy

Abstract

Microwave spectra have been observed with Fourier transform and cold jet expansion techniques in the 6−17 GHz range for trans-3,4-difluorocyclobutene, its two 13C1 modifications, two d1 modifications, and the perdeutero species. Watson-type Hamiltonians have been fit with a full set of quartic centrifugal distortion constants for all species except the d4 species. Complete structures fit with an rs/r0 treatment and an r0 treatment are in satisfactory agreement. Preferred rs/r0 results with Costain uncertainties in parentheses are 1.349(4) Å for the CC bond, 1.503(9) Å for the contiguous C−C bonds, 1.534(4) Å for the distant C−C bond, 1.398(6) Å for the C−F bond, 1.081(3) Å for the C−H bond, and 1.102(5) Å for the −C−H bond. Consistent with its C2 symmetry, the ring is slightly puckered, and the C−F bonds are roughly equatorial. Compared with the structure of cyclobutene, the structure of trans-3,4-difluorocyclobutene shows a modest lengthening of the CC bond and more significant decreases in the C−C bond lengths. These effects are consistent with observations for other fluorine-substituted rings in which contiguous fluorine atom substitution causes CC bond shortening and distant fluorine atom substitution causes CC bond lengthening. The CC bond adjustments in trans-3,4-difluorocyclobutene are, however, surprisingly similar to the adjustments observed for 3,3,4,4-tetrafluorocyclobutene.

Publisher

American Chemical Society

Publication Date

1-1-2002

Publication Title

Journal of Physical Chemistry

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://dx.doi.org/10.1021/jp020504e

Language

English

Format

text

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