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Citation: WANG Wen-feng, ZHANG Yong-fan, LI Jun-qian. DFT Study on the Mechanism of Cheletropic Addition of SO₂[J]. Acta Physico-Chimica Sinica, ;2006, 22(01): 82-85. doi: 10.3866/PKU.WHXB20060116 shu

DFT Study on the Mechanism of Cheletropic Addition of SO₂

1.
State Key Laboratory of Structural Chemistry, Department of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China

Received Date: 20 May 2005
Available Online: 15 January 2006

Cheletropic addition of sulfur dioxide to 2,4-hexadiene has been calculated by density functional theory(DFT) at the level of B3LYP/6-311+G**, the result of IRC calculation shows that the cheletropic addition is a concerted reaction. In reaction, each reactant gives its electrons in HOMO to the LUMO of other reactant simultaneously, which is different from the conditional mechanism of 4+2 cycloaddition. Before reaction, the difference of energy level between HOMO of sulfur dioxide and LUMO of 2,4-hexadiene is largish(8.4 eV), but in the course of reaction, the antibonding LUMO of 2,4-hexadiene turns into a bonding orbital and decreases its energy, so the electrons in HOMO of sulfur dioxide can flow into this orbital easily. The net result of the reaction is that sulfur dioxide transfers 0.23e negative charge to 2,4-hexadiene.
- Sulfur dioxide;2,4-hexadiene;Cheletropic addition;Mechanism;Orbital interaction
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DFT Study on the Mechanism of Cheletropic Addition of SO₂