Acta Chimica Sinica ›› 1999, Vol. 57 ›› Issue (3): 270-274. Previous Articles     Next Articles

Original Articles

用从头算研究Shilov反应的机理

丁涪江;张良辅;江丽葵   

  1. 中国科学院成都有机化学研究所.成都(610041)
  • 出版日期:1999-03-15 发布日期:1999-03-15

Ab initio study on the mechanism of Shilov reaction

Ding Fujiang;Zhang Liangfu;Jiang Likui   

  1. Chengdu Inst Organ Chem, CAS.Chengdu(610041)
  • Online:1999-03-15 Published:1999-03-15

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

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