speaker: ke an advisor: jun zhu 2012.11.30 a direct energetic measure of aromaticity based on a...
TRANSCRIPT
Speaker: ke AnAdvisor: Jun Zhu 2012.11.30
A Direct Energetic Measure of Aromaticity Based on a Cleavage of the Rings
in Cyclic Compounds
Abstract
+ 2 +
Homodesmotic reaction1
cyclic acyclicASE
1. Hehre, W. J.; Ditchfield, R.; Radom, L.; Pople, J. A. J. Am. Chem. Soc. 1970, 92, 4796–4801.
Outline
Introduction Results and discussion Conclusion Other work
Introduction
Various criteria: Geometry2
Energy3,4
Magnetism5
Electronic property
2. Krygowski, T. M.; Cyranski, M. K. Chem. Rev. 2001, 101, 1385-1419.3. Slayden, S. W.; Liebman, J. F. Chem. Rev. 2001, 101, 1541-1566.4. Cyranski, M. K. Chem. Rev. 2005, 105, 3773-3811.5. Chen, Z.; Wannere, C. S.; Corminboeuf, C.; Puchta, R.. Schleyer, P. v. R. Chem. Rev. 2005, 105, 3842-3888.
Results and Discussion
Benzene, naphthalene and pyridine were calculated at B3LYP/6-311+G* level, zero-point energy were applied.
6.Cyranski, M. K. Chem. Rev. 2005, 105, 3773–3811.
+ 2ASE = 33.3
+
+ 4ASE = 54.1
2 +
N
+ 2ASE = 29.1
+N
(33.26)
(51.3~54.36)
(31.06)
7.Krygowski, T. M.; Cyranski, M. K. Chem. Rev. 2001, 101, 1385-1419.
Pyrrole, furan and thiophene were calculated at MP2(fc)/6-311+G** level, zero-point energy were applied.
NH
+ 2ASE = 19.0
+NH
O+ 2
ASE = 16.5+
O
S+ 2
ASE = 19.4+
S
(20.67)
(14.87)
(18.67)
+ 4 2 +
+ 4 2 +ASE=46.5
ASE=54.1
Attention: ?
There are two trans π-conjugated configurations in the latter naphthalene.
cis trans-3.6kcal/mol
+ 4 2 +
+ 4 2 +
+ 4 + +
ASE=46.5
ASE=46.1
ASE=46.2
ASEcorr=53.7
ASEcorr=53.3
ASEcorr=53.4
Conclusion:The results above indicate that the cleavage method could be an effective way to evaluate the aromaticity of the cyclic compounds, especially for some cyclic unstrained π-conjugated rings
To examine the scope of the method
Os
PH3
PH3
Cl
Cl+
HOs
PH3
PH3
Cl
Cl+ Os
PH3
PH3
Cl
Cl+
HOs
PH3
PH3
Cl
Cl
ASE=12.3
Os
PH3
PH3
Cl
Cl
+ 2 Os
PH3
PH3
Cl
Cl+
ASE=15.4
Os
PH3
PH3
OC
OC
+H
Os
PH3
PH3
OC
OC+ Os
PH3
PH3
OC
OC
+H
Os
PH3
PH3
OC
OC
ASE=23.5
Os
PH3
PH3
OC
OC
+ 2 Os
PH3
PH3
OC
OC
+ASE=24.5
Os
PH3
PH3
Cl
ClOs
PH3
PH3
OC
OC
When CO replaces chloride ligand, there is a change from nonplanarity to planarity in osmabenzene. The dihedral in the former osmabenzene is 23.9 degrees. So its aromaticity is weaker than the latter one.
Conclusion
We conclude that the new method, based on the energy difference between the cyclic compound and the acyclic one, is able to produce a reliable result to evaluate the ASEs for both organic aromatics and metallaaromatics. In addition, it could be also applied to strained molecules if the strain energy can be evaluated separately.
Other Work
Antiaromatics:
pentalene cyclobutadiene
Nonaromatics:
Os
PH3
PH3
OC
OCosmacyclopentadiene
cyclopentadiene
+ 4 + +
+ 4 + 2
+ 2 2
ASE=-26.0
ASE=-29.6
ASE=-34.3
• This method can also be employed to evaluate the ASEs of antiaromatics.
• The ring strain energy(RSE) of the cyclobutadiene is taken into consideration.
Os
PH3
PH3
OC
OC+ 2 Os
PH3
PH3
OC
OC+
ASE=8.9
+ 2 +ASE= -0.3
However,
it seems to be that the osmacyclopentadiene is aromatic.
How could it happen?
Next Plans
To evaluate the ASEs of other strained molecules.
To extend this method to other organic aromatics and metallaaromatics.
To calculate the energies of the excited states both in aromatics and antiaromatics.