Advisor: Jun Zhu Speaker: Xuerui Wang Theoretical study on the interconversion of silabenzenes and their non-aromatic isomers via the [1,3]-substituent shift: aromaticity vs Bent's rule B ent's R ule A rom aticity A rom aticity B ent'rule Si O R X Si R O X G = -28.5 ~ 122.2 kcal m ol -1
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Advisor: Jun Zhu Speaker: Xuerui Wang Theoretical study on the interconversion of silabenzenes and their non-aromatic isomers via the [1,3]-substituent.
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Advisor: Jun Zhu Speaker: Xuerui Wang
Theoretical study on the interconversion of silabenzenes and their non-aromatic isomers via the
[1,3]-substituent shift: aromaticity vs Bent's rule
Bent's Rule Aromaticity
AromaticityBent' rule
SiO
RX
SiR OX
G = -28.5 ~ 122.2
kcal mol-1
Outline
Background
Computational Method
Results and Discussion
Conclusion4
1
2
3
Background
Text in here
Si
Ad
OTMS
TMS
TMSSi
Ad
OTMSTMS
TMS
hv
TMS = SiMe3Ad = 1-adamantyl
Figure 1.Photochemically Induced [1,3]-Trimethylsilyl Shift from Si to O Applied by Brook et al. to the Formation ofthe First Silene Stable at room temperature1. Brook, A. G.; Abdesaken, F.; Gutekunst, B.; Gutekunst, G.; Kallury, R. K. J. Chem. Soc., Chem. Commun. 1981,191. 2. Brook, A. G.; Nyburg, S. C.; Abdesaken, F.; Gutekunst, B.; Gutekunst, G.; Krishna, R.; Kallury, M. R.; Poon,Y. C.; Chang, Y. M.; Wong-Ng, W. J. Am. Chem. Soc. 1982, 104, 5667.
SiSiO
R3SiR3Si
R''R' R' R''
R'''R'''
OSiR3R3Si
R = Me or iPr
R' = H, Me, Et, iPr, tBu, OSiMe3
R'' = H, Me, Et, iPr, tBu
R''' = H, Me, tBu
Rouf, A. M.; Jahn, B. O.; Ottosson, H. Organometallics.2013, 32, 16.
Figure 2. Synthetic route to silabenzenes through the [1,3]-Si O TMS shift by Density functional theory (DFT) calculations
G= -11.1~ -22.6 kcal mol-1
Background
Rouf, A. M.; Jahn, B. O.; Ottosson, H. Organometallics.2013, 32, 16
driving force Aromaticity
G = 0.6 kcal/molSi SiO OSiMe3Me3Si
Me3SiMe3Si
Figure 3. [1,3]-Trimethylsilyl Shift Leading from 1,1-Bis(trimethylsilyl)-3,6-dimethylenesilacyclohexan-2-one to 1,1-Bis(trimethylsilyl)-3,6-dimethylene-2-(trimethylsiloxy) silacyclohex-1-ene
nonaromatic six membered ring
Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
silicon atom is reluctant to participate in bonding
Computational Method
Package :
Method :
basis sets :
Gaussian 09
M06-2X / B3LYP
6-311+G **
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.
DFT
Results and Discussion
Figure 4. The formation of silabenzenes through the [1,3]-Si→O substituent shift .
Bent’s rule : atomic s character tends to concentrate in orbitals that are directed toward electropositive groups and atomic p character tends to concentrate in orbitals that are directed toward electronegative groups.
(a) Bent, H. A. Chem. Rec.1961, 61, 275. (b) Zhu, J.; Lin, Z.; Marder, T. B. Inorg. Chem. 2005, 44, 9384.
1.928
1.481
1.346
1.472
1.343
1.8671.796
1.391
1.3971.396
1.393
1.770
1.934
1.482
1.346
1.474
1.344
1.8671.796
1.389
1.3971.397
1.394
1.775
SiSiO
H3SiH OHH3Si
G = -0.3SiSi
OH3Si
Me2N ONMe2H3Si
G = +46.8
a b
reluctance sp3
Results and Discussion
SiSiO
R1
X OXR1
X: H, NMe2, F, OMe, Cl, SMe, Me, GeH3, SiH3, AlH2
Set A: R1 = SiH3, Set B: R1 = Me
Figure 6. [1,3]-substituent shift for the formation of silabenzenes with various substituents.
SiOXH3Si
SiH2Si OX
X = H ISE = -25.3
X = NMe2 ISE = -28.3
Figure 5. The calculated ISE values of A1' and A2'.
NICS(0)zz -11.2 (X = H) -11.6 (X=NMe2)
Evaluate Aromaticity : ISE(isomerization stabilization energy) method and NICS( nucleus independent chemical shift) calculations
Results and DiscussionSilabenzene ΔG(298k)(kcal/mol) ΔSiC(ring) ΔCC(ring) NICS(0)zz Σα(Si)
X = F (a) X = OMe (b) X = Cl (c) X = NMe2 (d) X = SMe(e) X = Me(f) X = H(g) X = GeH3 (h) X = SiH3 (i) X = AlH2(j)
Results and Discussion
Figure 7. The plot of s character of Si to the Si-X σ bond vs ΔG
Results and Discussion
Figure 8. The plot of s character of Si to the Si-X σ bond vs reaction barriers (ΔG)
Results and Discussion
Figure 9. Plot of reaction free energies (ΔG) against the percentage of the s character of Si in the Si-X bonds by replacing the acyl group with methylene group in acylsilane..
Results and Discussion
Figure 10. Plot of reaction free energies (ΔG) against the percentage of the s character of Si in the Si-X bonds in nonaromatic system.