title: O-H...O versus O-H...S hydrogen bonding. 3. IR-UV double resonance study of hydrogen bonded complexes of p-cresol with diethyl ether and its sulfur analog.
abstract: In this work the hydrogen bonded complexes of diethyl ether (DEE) and diethyl sulfide (DES) with p-cresol (p-CR) were investigated. Only one conformer of the p-CR.DEE complex and three conformers of the p-CR.DES complex were found to be present under the supersonic jet expansion conditions. The conformational assignments were done with the help of IR-UV double resonance studies and ab initio calculations. The red shifts in the OH stretching frequency for the O-H...O and O-H...S hydrogen bonded complexes were quite close to each other. In fact, one of the p-CR.DES conformers showed a slightly larger red shift in the OH stretch than that in the p-CR.DEE conformer, which suggests that in this case sulfur is not a weak hydrogen bond acceptor as noted previously in case of the p-CR.H(2)O and p-CR.H(2)S complexes (Biswal et al. J. Phys. Chem. A 2009, 113, 5633). The natural bond orbital analysis also shows that the extent of overlap between sulfur lone pair orbitals (LP) and OH antibonding orbital (sigma*(OH)) was comparable to the oxygen (LP) and sigma*(OH) overlap, consistent with the similar magnitudes of the red shifts of OH stretch in the DES and DEE complexes. The computed binding energy of the p-CR.DES complex, however, was about 80% of the p-CR.DEE complex. The electron densities at the bond critical points indicated that the O-H...S interaction was weaker than the O-H...O interaction in this particular system also. The important finding of this study was that the IR red shifts in the H-bond donor X-H stretching frequency were not quite consistent with the computed binding energies and the atoms-in-molecules analysis contrary to the general understanding. Energy decomposition analysis suggests that O-H...S hydrogen bonding interaction is dispersive in nature and the dispersion contribution decreases with the increase in the length of the alkyl chain of the "S" hydrogen bond acceptor.
authors.affiliation: Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400 005, India.
authors.forename: Himansu S
authors.initials: HS
authors.lastname: Biswal
authors.forename: Sanjay
authors.initials: S
authors.lastname: Wategaonkar