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采用密度泛函理论(DFT)方法在B3LYP/6-311G(d,p)水平研究了硅苯与腈氧化物的1,3-偶极环加成反应的微观机理、势能剖面,考察取代基和四氢呋喃溶剂对反应势能剖面的影响。计算结果表明,所研究反应均以协同但非同步的方式进行,且总是Si-O键先于C-C键形成。硅苯分子中Si原子上的给电子和吸电子取代基均有利于反应的进行,而腈氧化物碳原子上的2,4,6-三甲基苯基取代基在热力学上对反应非常不利。四氢呋喃溶剂对所研究反应的势能剖面影响不大。
The microscopic mechanism and potential energy profile of the 1,3-dipolar cycloaddition reaction of silanol with nitrile oxide have been studied by density functional theory (DFT) at B3LYP / 6-311G (d, p) And tetrahydrofuran solvent on the potential energy profile of the reaction. The calculation results show that all the reactions studied are in a synergistic but non-synchronous manner, and the Si-O bond is always formed before the C-C bond. Both electron donating and electron withdrawing substituents on the Si atom of the silanol molecule favor the reaction while the 2,4,6-trimethylphenyl substituent on the carbon atom of the nitrile oxide is thermodynamically very detrimental to the reaction . Tetrahydrofuran solvent has little effect on the potential energy profile of the studied reaction.