关键词: 从头计算法, 反应机理, 烷烃, 甲烷, Shilov反应

The Shilov reaction, alkane oxidation using soluble platinum salts, holds a central place in alkane activation chemistry. The mechanism of the elementary interaction between CH~4 molecles and Pt(II) complexes deserves well attention: PtCl~2(H~2O)~2+CH~4→(CH~3)PtCl (H~2O)~2+H^++Cl^-. The real mechanism of this reaction still remains to be explained. We have looked at the oxidative addition and σ bond metathesis pathways for this reaction in this paper. Quantum chemical calculations have been carried out at RHF level using DZP basis set for all the intermediates and transition states in this reaction. Our study suggests that the Shilov reaction goes an oxidative addition of the C-H bond at Pt(II) and yield an alkylhydrodridoplatinum(IV) species.

Key words: AB INITIO CALCULATION, REACTION MECHANISM, ALKANE, METHANE