CEQUINOR   05415
CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Unidad Ejecutora - UE
artículos
Título:
Synthesis of the Novel species Methoxycarbonyl Perfluoromethane Disulfide, CH3OC(O)SSCF3: Structure in Solid State and Conformational Properties
Autor/es:
TORRICO VALLEJOS, SONIA; ERBEN, MAURICIO FEDERICO; BOESE, ROLAND; DELLA VÉDOVA, CARLOS OMAR
Revista:
NEW JOURNAL OF CHEMISTRY
Editorial:
ROYAL SOC CHEMISTRY
Referencias:
Año: 2010 vol. 34 p. 1365 - 1372
ISSN:
1144-0546
Resumen:
<!-- /* Font Definitions */ @font-face {font-family:SymbolPS; mso-font-alt:Symbol; mso-font-charset:2; mso-generic-font-family:roman; mso-font-pitch:variable; mso-font-signature:0 268435456 0 0 -2147483648 0;} @font-face {font-family:"CG Times (W1)"; panose-1:0 0 0 0 0 0 0 0 0 0; mso-font-alt:"Times New Roman"; mso-font-charset:204; mso-generic-font-family:roman; mso-font-format:other; mso-font-pitch:auto; mso-font-signature:515 0 0 0 5 0;} /* Style Definitions */ p.MsoNormal, li.MsoNormal, div.MsoNormal {mso-style-parent:""; margin:0cm; margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:12.0pt; font-family:"Times New Roman"; mso-fareast-font-family:"Times New Roman";} @page Section1 {size:612.0pt 792.0pt; margin:70.85pt 3.0cm 70.85pt 3.0cm; mso-header-margin:36.0pt; mso-footer-margin:36.0pt; mso-paper-source:0;} div.Section1 {page:Section1;} --> Pure methoxycarbonyl trifluoromethyl disulfide, CH3OC(O)SSCF3, has been prepared quantitatively by the reaction of CH3OC(O)SCl and Hg(SCF3)2. The conformational properties of the novel molecule have been studied by vibrational spectroscopy [IR(gas) and Raman(liquid)] and quantum chemical calculations (B3LYP and MP2 methods). The gaseous compound exhibits a conformational equilibrium at room temperature where the most stable form has C1 symmetry with a synperiplanar (syn) orientation of the C=O double bond with respect to the S-S disulfide bond. A second form is observed in the gaseous IR spectra corresponding to a conformer with the carbonyl bond C=O in antiperiplanar (anti) position with respect to the S–S single bond (ap). The structure of a single crystal of CH3OC(O)SSCF3 has been determined by X-ray diffraction analysis at low temperature using a miniature zone melting procedure. The crystalline solid (triclinic, P`1, a= 6.4698(5) Å, b= 9.0499(8) Å, c= 12.5700(11) Å, a= 97.219(6)º, b= 93.131(5)°, g= 96.888(5)º and Z= 4) consists exclusively of molecules with the synperiplanar conformation and the usual gauche orientation around the disulfide bond [f(CS-SC)=  91.02(25)º] is adopted. The geometrical parameters agree with those obtained from quantum chemical calculations.