1. Conversion of osmasilabenzyne into silylene complexes
Ying Huang（黄莹）
Adviser: Jun Zhu（朱军）

2. Outline
1. Backgroud
2. Conversion of osmasilabenzyne into silylene complexes
3. Conversion of the carbyne complex into the corresponding benzyne complex.
4. Conclusion and next to do

3. Backgroud Aromaticity Conjugation energy: 44.35kcal/mol
Tingbin Wen, Guochen Jia. Angew. Chem. Int. Ed. 2001, 40,1951
Guochen Jia, Zhenyang Lin. Organometallics, 2003,22,3898.

4. Electrophilic Substitution
The electrophilic Substitution usually occur at the C2 and C4 positions of the metallacycle
Zhenyang Lin, Guochen Jia. J. Am. Chem. Soc. 2011, 133, 18350

5. The effect of substituents
The calculated relative free energies and electronic energies (in parentheses) are given in kcal/mol.
Zhenyang Lin, Guochen Jia. Angew. Chem. Int. Ed. 2011, 50, 7295

6. DFT Package : Gaussian 03 Method: B3LYP basis sets : 6-31G *
LanL2DZ (Os (f) = 0.886)
(Si(f)= 0.262)
(P (f) =0.340))
The calculated relative free energies and electronic energies (in parentheses) are given in kcal/mol.

7. Occupied -molecular orbitals of osmasilabenzyne
HOMO-6
HOMO
HOMO-4
HOMO-9
HOMO-10
HOMO-12

8. Substituents effect

9. The Effect Of Substituents At The Ring
R=NO2
R=PH3
R= PMe3
R= PPh3

10. The effect of substituents at the ring
R=Me
R=n-pentyl
R=OMe

11. The Highest occupied molecular orbitals of osmasilabenzyne complexes
stable
NO2
OMe

12. The Highest occupied molecular orbitals of osmasilabenzyne complexes
NO2
stable
OMe

13. Substituents effect

14. The Effect Of Substituents At The Ring

15. Reason The charge of C1: -0.196 -0.184
The silyl group on the carbon adjacent to the carbyne carbon can prevent the protonation back to the corresponding osmabenzene through its polarization effect
Shengyong Yang, Journal of Organometallic Chemistry 2002,658 ,9.
The charge of Si: 0.240
0.158
0.118

16. The Highest occupied molecular orbitals of osmasilabenzyne complexesMe
t-Bu
TMS

17. The Effect Of Substituents At The Ring

18. The Effect Of Substituents At The Ring

19. The Lowest unoccupied molecular orbitals of osmasilabenzyne complexes
stable
NO2
OMe

20. Substituents effect

21. TS
LUMO

22. Detail 1
R=NO2
R=PH3
R= PMe3
R= PPh3

23. Detail 1
can PH3 replace PMe3 ?

24. Detail 1 R

25. Detail 2

26. The Effect Of Substituents At The Ring

27. The Effect Of Substituents At The Ring

28. conclusion
Theoretical calculations at the B3LYP level of density functional theory have been carried out to study the migratory insertion reactions from osmasilabenzyne complexes to silylene complexes.
The effect of substituents at the ring on the stabilities has also been explored, we found that the effect of substituents in the six-membered ring play important roles in determining the relative stabilities.
Furthermore, the possible path from some silylidyne complexes to the silylene complexes have found.
Next to do
Compute the ELF(electron localization function) to find the reason why the osmasilabenzyne complex is less stable than the osmabenzyne complex.
Explore the answers about these problems which have mentioned just now.
Realize the Conversion of silylene complexes into osmasilabenzyne.

29. Thanks for your attention