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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 WangAdvisor : Jun Zhu
Dec. 27. 2013
Outline
11
3
Background
2
2
3 Summary and Future work
Results and Discussion
3
Background
Interpaly of aromaticity and Bent's rule
SiSiOR
X OXR
X = H, NMe2, F, OMe, Cl, SMe, Me, GeH3, SiH3, AlH2
Set A: R = SiH3Set B: R = Me
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
Background
examine the scope of our findingsSilabenzene
(X) ΔG ΔG' ΔG'-ΔG
A1' (H)A2' (NMe2)
-0.346.8
27.674.8
27.928.0
A3' (Me)A4' (SMe)A5' (Cl)A6' (OMe)A7' (F)A8' (GeH3)A9' (SiH3)A10' (AlH2)
B1' (H)B2' (NMe2)
B3' (Me)B4' (SMe)B5' (Cl)B6' (OMe)B7' (F)B8' (GeH3)B9' (SiH3)B10' (AlH2)
17.838.177.284.8117.8-0.8-16.1-29.32.354.522.342.481.590.2122.20.1-14.8-28.5
46.167.0105.9114.0147.426.812.5-2.232.983.951.173.3114.1121.8153.830.015.6-0.2
28.328.928.729.229.627.628.631.530.629.428.830.932.631.631.629.930.428.7
aromaticity can be evaluated quantitatively
5
BackgroundHistory 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-butadiene1.
2. 1982 Spectroscopic detection of 1,4-dialkylgermabenzenes2.
3. 2002 First stable germabenzene3.
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
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
Results and Discussion
Figure 3.The plot of s character of Ge to the Ge-X σ bond vs reaction energies(ΔG)
GeOX
RGe
OXRG
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) ΔG ΔG' ΔG'-ΔG
A1' (H)A2' (NMe2)
1.338.2
28.366.9
27.028.7
A3' (Me)A4' (SMe)A5' (Cl)A6' (OMe)A7' (F)A8' (GeH3)A9' (SiH3)A10' (AlH2)
B1' (H)B2' (NMe2)
B3' (Me)B4' (SMe)B5' (Cl)B6' (OMe)B8' (GeH3)B9' (SiH3)B10' (AlH2)
17.437.376.473.3106.43.0-12.0-23.42.844.621.542.880.177.64.8-10.2-23.5
43.266.0106.4102.1135.530.417.1-334.174.749.273.3112.3109.634.518.56.3
25.828.730.028.829.127.429.120.431.330.127.730.532.232.029.728.729.8
GeOX
RGe
OXRG
28.6
9
Results and Discussion
Figure 5.The plot of s character of Sn to the Sn-X σ bond vs reaction energies(ΔG)
SnOX
RSn
OXRG
10
Results and Discussion
SnOX
RSn
OXRG
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
Si
[Os]G
OXR
Si
[Os]
OXR
11Figure 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
Results and Discussion
nme 45. 1 76. 6 31. 5sme 39. 4 72. 9 33. 5me 16. 6 47. 8 31. 2h -3. 6 24. 3 27. 9ge -10. 1 28. 7 38. 8si -18. 5 18. 4 36. 9al -19. 9 6. 4 26. 3
me 12. 6 50. 1 37. 5h -6. 3 28. 6 34. 9ge -14. 6 24. 3 38. 9si -23. 1 13. 7 36. 8al -24. 5 -2. 7 21. 8nme 44. 6 82. 2 37. 6
R=SiH3 ΔG ΔG' ΔG'-ΔG
R=Me ΔG ΔG' 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
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
Organophosphorus
compounds
14
pesticide
flame retardant
medicine
antibacterial agents
enzyme inhibitors
anti HIV agents
Experiments
?P
OEtO
EtOH
P
OEtO
EtO
15
Entry initiator eq solvent T(oC) t[h]NMR yield
[%]
1 Mn(OAc)3 2.2 HOAc 80 12 15
2 Mn(OAc)3 2.2 DMF 80 12 5
3 Mn(OAc)3 2.2 THF 80 12 trace
4 AgNO3 0.5 DMF 80 12 trace
5 AIBN 1.2 THF 80 12 trace
Condition Optimization
16
PO
OEt
EtO
Et2OP
O
Et2OP
O
Mn3+
Mn2+
Et2OP
O
+
- H+
HPO
OEt
EtO
Mn3+
Mn2+
Et2OP
O
Proposed Reaction Mechanism
17
PO
OEt
EtO
Et2OP
O
Mn3+
Mn2+
Et2OP
O
AcO-
Et2OP
O
OAc By product
1. Yang et al, Angew. Chem. Int. Ed. 2013, 52, 3972.2. Zou et al, Synthesis 2013, 45, 1529 .
18
• Thank you for your attention!
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