Unimolecular Chemistry of Methyl Formate Cation Radical. A Combined Theoretical and Experimental Study
Unimolecular Chemistry of Methyl Formate Cation Radical. A Combined Theoretical and Experimental Study
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甲酸甲酯阳离子自由基的单分子化学。
DOI：
10.1002/chin.199234096
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发表时间：
1992
期刊：
影响因子：
--
通讯作者：
H. Schwarz
中科院分区：
文献类型：
--
作者：
N. Heinrich;T. Drewello;P. Burgers;J. C. Morrow;Jochen Schmidt;W. Kulik;J. K. Terlouw;H. Schwarz
采用MP3/6-31G**//6-31G*+ZPVE水平的分子轨道计算和质谱实验相结合的方法，研究了甲酸甲酯阳离子自由基(I)的单分子化学性质。最小能量需求路径对应于CO的损失，通过一个显著的原子特异性过程产生ch3oh * +。计算表明，反应通过氢桥络合物ch3oh…C≡O进行。+ (5)
The unimolecular chemistry of solitary methyl formate cation radical (I) has been studied by a combination of ab initio molecular orbital calculations executed at the MP3/6-31G**//6-31G*+ZPVE level of theory and mass spectrometry based experiments. The minimal energy requirement path corresponds to the loss of CO to produce CH 3 OH* + via a remarkably atom-specific process. The calculations indicate that the reaction proceeds via the hydrogen-bridged complex CH 3 OH...C≡O .+ (5)