Cycloaddition mechanism for the resin-OsO_4-catalyzed of styrene: A DFT study  

作　　者：ZHANG XingHui1, WANG KeTai1 & FANG Ran2 1 College of Chemical Engineering, Gansu Unite University, Lanzhou 730000, China 2 College of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China 

出　　处：《Science China Chemistry》2008年第1期19-24,共6页中国科学（化学英文版）

摘　　要：The postulated intermediates in the base-free and base-assisted addition of OsO4 to styrene have been investigated at the B3LYP/6-311G** level of the theory. N(CH3)2(Ph) was chosen as the base of the resin-OsO4. According to our model calculations the [2+3] addition was found to be favorable with an activation of <45.00 kJ/mol. In contract, the reaction barriers for the [2+2] cycloaddition remain high (>155.00 kJ/mol). In addition, the electronic structure analysis of the molecules was carried out by na- ture bond orbital (NBO). The computational results were in reasonable agreement with experimental results.The postulated intermediates in the base-free and base-assisted addition of OsO4 to styrene have been investigated at the B3LYP/6-311G** level of the theory. N(CH3)2(Ph) was chosen as the base of the resin-OsO4. According to our model calculations the [2+3] addition was found to be favorable with an activation of <45.00 kJ/mol. In contract, the reaction barriers for the [2+2] cycloaddition remain high (>155.00 kJ/mol). In addition, the electronic structure analysis of the molecules was carried out by na- ture bond orbital (NBO). The computational results were in reasonable agreement with experimental results.

关 键 词：CYCLOADDITION resin-OsO4 density FUNCTIONAL theory 

分 类 号：O643.32[理学—物理化学]