Microwave rotational spectra and structures of 2-fluoropyridine and 3-fluoropyridine.

The ground state rotational spectra of 2-fluoropyridine and 3-fluoropyridine have been investigated using both Fourier transform microwave (FTMW) and chirped pulse Fourier transform microwave (cp-FTMW) spectroscopies. In addition to the parent species, the spectra of the (13)C and (15)N singly substituted isotopologues were recorded in the 8-23 GHz region in natural abundance. The rotational constants determined for the seven isotopologues of each were used to calculate relevant geometric parameters including the bond distances and angles of the pyridine ring backbone. The derived structures show a more pronounced deviation from the pyridine ring geometry when the fluorine substituent is ortho to nitrogen which is consistent with ab initio predictions at various levels of theory. Analysis of the (14)N hyperfine structure provided an additional source of information about the electronic structure surrounding the nitrogen atom as a function of fluorine substitution. Together, the experimental results are consistent with a bonding model that involves hyperconjugation whereby fluorine donates electron density from its lone pair into the π-system of pyridine.