posted on 2013-07-11, 00:00authored byLuis A. Ramos, Sonia
E. Ulic, Rosana M. Romano, Yury V. Vishnevskiy, Norbert W. Mitzel, Helmut Beckers, Helge Willner, Shengrui Tong, Maofa Ge, Carlos O. Della Védova
Chlorodifluoroacetyl isothiocyanate,
ClF2CC(O)NCS, was
synthesized by the reaction of ClF2CC(O)Cl with an excess
of AgNCS. The colorless product melts at −85 °C, and its
vapor pressure follows the equation ln p = −4471.1
(1/T) + 11.35 (p [atm], T [K]) in the range −38 to 22 °C. The compound
has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry),
by liquid Raman, by 19F and 13C NMR, gas UV–vis,
and photoelectron spectroscopy (PES), by photoionization mass spectrometry
(PIMS), and by gas electron diffraction (GED). The conformational
properties of ClF2CC(O)NCS have been analyzed by joint
application of vibrational spectroscopy, GED and quantum chemical
calculations. The existence of two conformers has been detected in
the gas and liquid phases, in which the C–Cl bond adopts a
gauche orientation with respect to the CO group; the CO
group is in syn- or anti-position with respect to the NC double
bond of the NCS group. The computed ΔG°
difference between these two gauche–syn and gauche–anti
forms is ΔG° = 0.63 kcal mol–1 in the B3LYP/6-31G(d) approximation. The most significant gas-phase
structural parameters for gauche–syn ClF2CC(O)NCS
are re(NCS) 1.559(2) Å, re(NCS) 1.213(2) Å, re(NC) 1.399(7) Å, re(CO) 1.199(2) Å, and ∠e(CNC) 134.7(13)°. Photolysis of ClF2CC(O)NCS
using an ArF excimer laser (193 nm) mainly yields ClF2CNCS,
CO, and ClC(O)CF2NCS. The valence electronic properties
of the title compound were studied using PES and PIMS. The experimental
first vertical ionization energy of 10.43 eV corresponds to the ejection
primarily of the sulfur lone-pair electrons of the in-plane nonbonding
orbital on the NCS group.