Conformational behavior of CH3OC(O)SX (X= CN and SCN) pseudohalide congeners. A combined experimental and theoretical study

TORRICO VALLEJOS, SONIA; ERBEN, MAURICIO FEDERICO; GE, MAO-FA; WILLNER, HELGE; DELLA VÉDOVA, CARLOS OMAR

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Año: 2010 vol. 114 p. 3703 - 3712

1089-5639

Pure methoxycarbonylsulfenyl cyanide, CH3OC(O)SCN (I), and methoxycarbonylsulfenyl thiocyanate, CH3OC(O)SSCN (II), were prepared by reacting liquid CH3OC(O)SCl with either AgCN or AgSCN, respectively. Compounds I and II were characterized by 1H NMR, CG-MS, and vibrational (FTIR and FTRaman) techniques. The conformational properties have been studied by using vibrational spectroscopy [infrared (gaseous, liquid, and Ar matrix isolated), Raman (liquid) spectroscopy] together with quantum chemical calculations at the B3LYP and MP2 methods with the extended 6-311++G** and aug-cc-pVTZ basis sets. Compound I exhibits a conformational equilibrium at room temperature having the most stable form Cssymmetry with a synperiplanar (syn) orientation of the carbonyl double bond (CdO) with respect to both the CH3O- and -SCN groups (syn-syn). Several bands assigned to a second conformer have been observed in the IR matrix spectra. This rotamer presents an antiperiplanar orientation of the thiocyanate group (syn-anti). Evaluating the equilibrium compositions at different temperatures by quenching the gas phase mixtures as Ar matrices allowed us to determine the conformational enthalpy difference ΔH0= H0 (syn-anti) - H0 (syn-syn) ) 0.80(18) kcal mol-1. A similar conformational behavior has been determined for compound II. Thermodynamicproperties were also computed at the high-level G2MP2 and G3 model chemistry methods. The importance of mesomeric (resonance) and anomeric (hyperconjugation) electronic interaction in the conformational behavior is evaluated by using the NBO approach for both species.