MICROWAVE SPECTRUM AND ROTATIONAL ISOMERISM OF ETHYL NITRITE

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1977

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Ohio State University

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The microwave spectrum of ethyl nitrite, $C_{2}H_{5}ONO$ shows the presence of at least three rotational isomers. Two rotamers correspond to cis-trans $(\tau_{1}(ON-OC) = 0^\circ, \tau_{2}(NO-CC) = 180^\circ)$ and cis-gauche $(\tau_{1} = 0^\circ, \tau_{2} \approx 90^\circ)$ structures. Relative intensity measurements show the cis-gauche form to be less stable by $233 \pm 50 \ cm^{-1}$. A moderately strong spectrum of a third rotamer (K = - 0.98) has been assigned a trans-gauche structure $(\tau_{1}= 180^\circ \tau_{2}, \approx 90^\circ)$. The spectrum of this rotamer shows no obvious tunneling effects with the other, equivalent guache form. This rigidity contrasts with the very low methyl group barrier in trans methyl nitrite $(V_{3} = 30 \ cal \ mol^{-1}).^{1}$ Searches for a planar heavy atom trans ethyl nitrite rotamer are currently in progress.

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$^{1}$ M. J. Corkill, A. P. Cox, and P. H. Turner (to be published).
Author Institution: Mallinckrodt Chemical Laboratories, Harvard University

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