Vibrational properties of some elusive members of the RNSO family: CF₃NSO and SF₅NSO

详细信息    查看全文

• 作者：Andrea Flores Antognini ; Heinz Oberhammer ; Edgardo H. Cutin ; Norma L. Robles
• 关键词：N-(trifluoromethyl)sulfinylimine ; N-(pentafluorsulfanyl)sulfinylimine ; Vibrational spectra ; Quantum chemical calculations ; Conformational properties
• 刊名：Journal of Molecular Structure
• 出版年：2012
• 出版时间：12 September, 2012
• 年：2012
• 卷：1023
• 期：Complete
• 页码：75-80
• 全文大小：469 K

文摘

The vibrational spectra of N-(trifluoromethyl)sulfinylamine, CF₃NSO and N-(pentafluorsulfanyl)sulfinylamine, SF₅NSO have been recorded and assigned. According to quantum chemical calculations (B3LYP and MP2 with 6-31G(d) and 6-311+G(df) basis sets) the sterically unfavorable syn (Z-) conformers are 2.6-4.1 kcal/mol (CF₃NSO) and 3.1-4.6 kcal/mol (SF₅NSO) lower in free energy than the anti conformers. Such ¦¤G¡ã values determine an equilibrium of 98.8 % (syn) and 1.2 % (anti) for CF₃NSO, and ¡Ö99 % (syn) and < 1 % (anti) for SF₅NSO (B3LYP and MP2 with 6-311+G(df) basis set). The presence of a single conformer is confirmed by the vibrational spectra. The syn structure of RNSO compounds is stabilized by strong anomeric effects between the N and S electron lone pairs and the opposite NR and SO ¦Ò^* bonds. The bonding properties of some RNSO and RNS(O)F₂ compounds are compared.