1. Activation of Methane and Toluene by Rhodium(Ⅱ) Porphyrin Complexes
Bradford B. Wayland*, Sujuan Ba, and Alan E. Sherry
Date:

2. Background Oxidative addition σ -bond metathesis
Addition to M=X groups
Cummins, C. C.; Baxter, S. M.; Wolczanski, P.T. J . Am. Chem. Soc.1988, 110, 8731

3. Reactions of (TMP)Rh

4. Thermodynamic and kinetic-mechanistic studies

5. Thermodynamic and kinetic-mechanistic studies
Second order

6. Thermodynamic and kinetic-mechanistic studies

7. Reactions about benzene

8. Reactions of [(TXP)Rh]2

9. Thermodynamic and kinetic-mechanistic studies

10. Thermodynamic and kinetic-mechanistic studies

11. Reactions about benzene

12. Reactions of [(OEP)Rh]2

13. Reactions with toluene

14. Reactions about toluene

15. Reactions about toluene

16. Rh-Rh bond energy

17. Thermodynamic studies for methane activation
M-M
CH3-H
(M-H)+(M-CH3)
(TMP)Rh
-13
105
118
[(TXP)Rh]2 12
117
Unit: kcal/mol
(OEP)Rh-H 62 kcal/mol

18. Kinetic-mechanistic studies for methane activation
Obvious isotope effects
Small enthalpies

19. Kinetic-mechanistic studies for methane activation

20. Selectivity
Rh(Ⅲ) react with Aromatic C-H Bond thermodynamically favored Rh(Ⅱ) no reaction with Aromatic C-H Bond kinetically inhibited

21. Overview No reaction with aromatic C-H React with alkyl C-H bonds
Two metalloradicals
Steric effect

22. The End
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