1. Theoretical study on the interconversion of X-benzenes （ X=Ge 、 Sn ） and their non-aromatic isomers via the [1,3]- substituent shift: Interpaly of aromaticity and Bent's rule Speaker: Xuerui Wang Advisor : Jun Zhu Dec. 27. 2013

2. Outline 1 1 3 Background 2 2 3 Summary and Future work Results and Discussion

3. 3 Background Interpaly of aromaticity and Bent's rule Figure 2. The plot of s character of Si to the Si-X σ bond vs reaction barriers (ΔG  ) Figure 1.The plot of s character of Si to the Si-X σ bond vs reaction energies(ΔG)

4. 4 Background examine the scope of our findings Silabenzene (X)ΔGΔG'ΔG'-ΔG A1 ' (H) A2 ' (NMe 2 ) -0.3 46.8 27.6 74.8 27.9 28.0 A3 ' (Me) A4 ' (SMe) A5 ' (Cl) A6 ' (OMe) A7 ' (F) A8 ' (GeH 3 ) A9 ' (SiH 3 ) A10 ' (AlH 2 ) B1 ' (H) B2 ' (NMe 2 ) B3 ' (Me) B4 ' (SMe) B5 ' (Cl) B6 ' (OMe) B7 ' (F) B8 ' (GeH 3 ) B9 ' (SiH 3 ) B10 ' (AlH 2 ) 17.8 38.1 77.2 84.8 117.8 -0.8 -16.1 -29.3 2.3 54.5 22.3 42.4 81.5 90.2 122.2 0.1 -14.8 -28.5 46.1 67.0 105.9 114.0 147.4 26.8 12.5 -2.2 32.9 83.9 51.1 73.3 114.1 121.8 153.8 30.0 15.6 -0.2 28.3 28.9 28.7 29.2 29.6 27.6 28.6 31.5 30.6 29.4 28.8 30.9 32.6 31.6 29.9 30.4 28.7 aromaticity can be evaluated quantitatively

5. 5 Background History of Germabenzenes 1.1980 Märkl et al. confirmed the existence of 1,4-di-tert -butyl-germabenzene indirectly supported by the formation of its [2 + 2] dimer and the trapping reaction with 2,3-dimethyl-1,3-butadiene 1. 2.1982 Spectroscopic detection of 1,4-dialkylgermabenzenes 2. 3.2002 First stable germabenzene 3. 1. G. Märkl, D. Rudnick, Tetrahedron Lett. 1980, 21, 1405. 2. G. Märkl, D. Rudnick, R. Schulz, A. Schweig, Angew. Chem. 1982, 94, 211; Angew. Chem. Int. Ed. Engl. 1982, 21, 221. 4. N. Nakata, N. Takeda, N. Tokitoh, J. Am. Chem. Soc. 2002, 124, 6914.

6. 6 Computational detail Package : Method : Basis sets : Gaussian 09 M06-2X 6-311+G ** ( C 、 H 、 O 、 Si 、 Ge) aug-cc-pVTZ-PP ( Sn ) 1.(a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200. (c) Lee, C.; Yang, W.; Parr, G. Phys. ReV. B 1988, 37, 785. 2. Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. 3. Frisch, M. J. et al. Gaussian, Inc., Wallingford CT, 2010. Background stable and neutral stanna aromatic compounds

7. 7 Results and Discussion Figure 3.The plot of s character of Ge to the Ge-X σ bond vs reaction energies(ΔG)

8. 8 Results and Discussion Figure 4.The plot of s character of Ge to the Ge-X σ bond vs reaction energies(ΔG) in nonaromatic system Silabenzene (X) ΔGΔG'ΔG'-ΔG A1 ' (H) A2 ' (NMe 2 ) 1.3 38.2 28.3 66.9 27.0 28.7 A3 ' (Me) A4 ' (SMe) A5 ' (Cl) A6 ' (OMe) A7 ' (F) A8 ' (GeH 3 ) A9 ' (SiH 3 ) A10 ' (AlH 2 ) B1 ' (H) B2 ' (NMe 2 ) B3 ' (Me) B4 ' (SMe) B5 ' (Cl) B6 ' (OMe) B8 ' (GeH 3 ) B9 ' (SiH 3 ) B10 ' (AlH 2 ) 17.4 37.3 76.4 73.3 106.4 3.0 -12.0 -23.4 2.8 44.6 21.5 42.8 80.1 77.6 4.8 -10.2 -23.5 43.2 66.0 106.4 102.1 135.5 30.4 17.1 -3 34.1 74.7 49.2 73.3 112.3 109.6 34.5 18.5 6.3 25.8 28.7 30.0 28.8 29.1 27.4 29.1 20.4 31.3 30.1 27.7 30.5 32.2 32.0 29.7 28.7 29.8 28.6

9. 9 Results and Discussion Figure 5.The plot of s character of Sn to the Sn-X σ bond vs reaction energies(ΔG)

10. 10 Results and Discussion Figure 6.The plot of s character of Sn to the Sn-X σ bond vs reaction energies(ΔG) in nanaromatic system aromaticity can not be evaluated quantitatively

11. 11 Figure 8. Plot of reaction free energies (ΔG) against the percentage of the s character of Si in the Si-X bonds in the osmasilabenznes. Results and Discussion

12. 12 Results and Discussion R=SiH3 ΔGΔG'ΔG'-ΔG R=Me ΔGΔG'ΔG'-ΔG 33.4 Figure 9. Plot of reaction free energies (ΔG) against the percentage of the s character of Si in the Si-X bonds.

13. 13 1. The contribution from aromaticity can be evaluated quantitatively in such rearrangement. 2. Bent's rule plays an important role in both the thermodynamics and kinetics of the rearrangement. 3. Our findings could be a useful guide to the synthesis of X-benzenes (X = Ge 、 Sn). Summary

14. 14 Organophosphorus compounds 14 pesticide flame retardant medicine antibacterial agents enzyme inhibitors anti HIV agents Experiments

15. ？ 15 Entryinitiator eq solventT( o C)t[h] NMR yield [%] 1 Mn(OAc) 3 2.2HOAc801215 2 Mn(OAc) 3 2.2DMF80125 3 Mn(OAc) 3 2.2THF8012trace 4 AgNO 3 0.5DMF8012trace 5 AIBN1.2THF8012trace Condition Optimization

16. 16 Proposed Reaction Mechanism

17. 17 By product 1.Yang et al, Angew. Chem. Int. Ed. 2013, 52, 3972. 2. Zou et al, Synthesis 2013, 45, 1529.

18. 18 Thank you for your attention ！