Conformational Transferability of the Sulfenyl Carbonyl Group -SC(O)- in Cyclic Thioesters

NAHIR Y. DUGARTE; MAURICIO F. ERBEN; EVAMARIE HEY-HAWKINS; PETER LÖNNECKE; SVEN STADLBAUER; MAO-FA GE; OSCAR E. PIRO; GUSTAVO A. ECHEVERRíA; CARLOS O. DELLA VEDOVA

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2013 vol. 117 p. 5706 - 5714

1089-5639

The molecular and crystal structure of two dithiolactones (formally dimers of å-caprothiolactone and ù-hexadecathiolactone) have been determined by X-ray diffraction at low temperature, revealing that the thioester group is planar with a synperiplanar orientation of the C=O double bond with respect to the S-C single bond.This conformational behavior is in contrast to that found for the smaller cyclic members ofthis family, where the antiperiplanar conformation is enforced. It is hypothesized thatstrain effects play a major role for the energy balance in the conformational preference. Inthis context, the molecular, vibrational (infrared and Raman), and electronic properties ofå-caprothiolactone have also been analyzed by using a combined experimental, includinggas-phase helium I photoelectron spectroscopy, and computational approach.