The Effect of Pressure on the Electrophilic Substitution Reaction of Tetramethyltin with Iodine

Tetramethyltin과 Iodine의 친전자 치환반응에 대한 압력의 영향

  • 권오천 (한양대학교 자연과학대학 화학과) ;
  • 이훈영 (한양대학교 자연과학대학 화학과)
  • Published : 1993.06.20


Ultraviolet spectrophotometric investigation has been carried out on the system of iododestannylation iodine and tetramethyltin in methanol. The transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine. From there, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}\;and\;{\Delta}G^{\neq}$) were obtained. The activation volumes and activation compressibility coefficients were both negativity. The activation enthalpies were positive and activation entropies had large negative values. From these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_E2$ mechaenism and weakened $S_E2$ mechanism nature by increasing pressure.



  1. Molecular Complexes R. S. Mulliken;Person
  2. Molecular Complexes M. Tamres;R. Foster(ed.)
  3. Bull. Chem. Soc. Japan v.52 R. Kuwae;T. Tanaka;K. Kawakaki
  4. Bull. Chem. Soc. Japan v.48 R. Kuwae;T. Tanaka;K. Kawakaki
  5. J. Phys. Chem. v.84 S. Fukuzumi;J. K. Kochi
  6. J. Phys. Chem. v.85 S. Fukuzumi;J. K. Kochi
  7. J. Am. Chem. Soc. v.88 J. B. Hyne;H. S. Golinkin;W. G. Laidlaw
  8. Tetra. Lett. v.35 N. S. Issacs;K. Javaid
  9. Tetra. Lett. v.25 N. S. Issacs;K. Javaid
  10. J. Basic Science v.7 O. C. Kwun;K. J. Choi;Y. H. Lee
  11. J. Korean Chem. Soc. v.37 O. C. Kwun;J. B. Kyong;Y. H. Lee
  12. Physicochemical Calculation(2nd Ed.) E. A. Guggenheim;J. E. Pure
  13. Prog. Phys. Org. Chem. v.11 M. H. Abraham
  14. Can. J. Chem. v.49 M. J. Mackinon;J. B. Hyne
  15. Inter. J. Chem. Kinetics v.1 K. J. Laidler;R. Martin
  16. Proceedings of NATO Advanced Study Institute High Pressure Chemistry H. Kelm;D. A. Palmer
  17. Bull. Chem. Soc. Japan v.45 Y. Kondo;M. Ohnishi
  18. Liquid Phase High Pressure Chemistry N. S. Issacs
  19. J. Korean Chem. Soc. v.30 O. C. Kwun;J. B. Kyong
  20. J. Korean Chem. Soc. v.32 K. J. Choi;Y. H. Lee;J. B. Kyong;J. R. Kim
  21. Trans. Faraday Soc. v.64 D. A. Lown;H. R. Thirsh;L. W. Jones
  22. Bull. Chem. Soc. Japan v.40 Y. Kondo;H. Tojima;N. Tokura
  23. Bull. Chem. Soc. Japan v.43 T. Matsui;N. Tokura
  24. J. Org. Chem. v.20 J. E. Leffer
  25. Molecular Complexes v.1 A. K. Colter;J. M. R. Dack;R. Foster(ed.)
  26. The Theory of Rate Reaction S. Glasstone;K. J. Laidler;H. Eyring
  27. Organic Charge-Transfer Complexes R. Foster