10.1021/jo701543g.s005
Sonia Torrico Vallejos
Sonia Torrico
Vallejos
Mauricio F. Erben
Mauricio F.
Erben
Helge Willner
Helge
Willner
Roland Boese
Roland
Boese
Carlos O. Della Védova
Carlos
O. Della Védova
Preparation and Properties of Methoxycarbonylsulfenyl Isocyanate,
CH<sub>3</sub>OC(O)SNCO
American Chemical Society
2007
vibrational spectroscopy
novel species
metathesis reaction
OC
form C S symmetry
isocyanate group
synperiplanar conformation
Methoxycarbonylsulfenyl Isocyanate
UV
quantum chemical calculations
FTIR
MP 2 methods
CO
IR spectrum
1 H
CS
bond synperiplanar
CH
compound exhibits
13 C NMR
B 3LYP
molecule
room temperature
2007-11-23 00:00:00
Figure
https://acs.figshare.com/articles/figure/Preparation_and_Properties_of_Methoxycarbonylsulfenyl_Isocyanate_CH_sub_3_sub_OC_O_SNCO/2972821
Pure methoxycarbonylsulfenyl isocyanate, CH<sub>3</sub>OC(O)SNCO, is quantitatively prepared by the metathesis
reaction between CH<sub>3</sub>OC(O)SCl and AgNCO. This novel species has been obtained in its pure form and
characterized by <sup>1</sup>H and <sup>13</sup>C NMR, UV−vis, FTIR, and FT-Raman spectroscopy. The conformational
properties of the gaseous molecule have been studied by vibrational spectroscopy and quantum chemical
calculations (B3LYP and MP2 methods). The compound exhibits a conformational equilibrium at room
temperature having the most stable form <i>C</i><i><sub>S</sub></i> symmetry with the CO double bond synperiplanar with
respect to the S−N single bond. A second form was observed in the IR spectrum and corresponds to a
conformer possessing the C−S bond antiperiplanar with respect to the NC double bond of the isocyanate
group. The structure of a single crystal of CH<sub>3</sub>OC(O)SNCO was determined by X-ray diffraction analysis
at low temperature using a miniature zone melting procedure. The crystalline solid (triclinic, <i>P</i>1̄, <i>a</i> =
8.292(6) Å, <i>b</i> = 9.839(7) Å, <i>c</i> = 11.865(8) Å, α = 67.290(2)°, β = 71.5570(10)°, γ = 83.4850(10)° and
<i>Z</i> = 6) shows the presence of molecules having exclusively a synperiplanar conformation with respect
to the three φ(CO−CO), φ(OC−SN), and φ(CS−NC) dihedral angles.