The phenylsulfenium cation: Electronic structure and gas-phase reactivity

✍ Scribed by Olga Bortolini; Alessandra Guerrini; Vittorio Lucchini; Giorgio Modena; Lucia Pasquato

• Book ID: 104262044
• Publisher: Elsevier Science
• Year: 1999
• Tongue: French
• Weight: 207 KB
• Volume: 40
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(99)01261-7

✦ Synopsis

The energies and the geometries of the phenylsulfenium cation (PhS +) in the singlet and triplet states have been optimized ab initio at the MP216-31G*IIMP216-31G* level. The (1A) PhS + state is more stable by 63.0 kJ mol "1 than the (3A) PhS + state. The PhS + ion reacts in the gas-phase with ethylene and carbon monoxide affording the addition products [PhS+CO]+ and [PhS+CH2CH2] + respectively. Ab initio calculations and MS/MS spectra suggest that the additions of CH2CH 2 and CO occur at the sulfur center.