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Rotational Spectroscopic and Ab Initio Investigation of the Rotamer Geometries of 2‑Fluoroanisole and 3‑Fluoroanisole
journal contribution
posted on 2020-03-09, 17:07 authored by Katrina Bergmann, Jennifer van WijngaardenThe
rotational spectra of 2-fluoroanisole and 3-fluoroanisole were
investigated using Fourier transform microwave spectroscopy in the
4–26 GHz range. Assigned transitions correspond to the lowest
energy rotamer for 2-fluoroanisole which has the O–CH3 group directed away (anti) from the fluorine substituent
whereas for 3-fluoroanisole, the spectrum is consistent with the presence
of two rotamers arising from syn and anti orientations of the methoxy moiety relative to fluorine. Ab initio calculations at the MP2/cc-pVTZ level were used
to estimate the equilibrium (re) geometries
of the three observed rotamers. Their assignments were confirmed through
the observation of the rotational transitions of eight minor isotopologues
(13C and 18O) in natural abundance for each
species. The mass dependence (rm(1)) structures derived using the experimentally determined rotational
constants compare favorably with the ab initio estimates.
The resulting sets of geometric parameters suggest that the aromatic
ring backbone is distorted by the introduction of the angular methoxy
substituent, with a tendency to induce bond length alternation around
the ring, and by the electron withdrawing effects of fluorine.