Matrix Isolation Infrared Spectroscopic and Density Functional Study of the Mechanism of the Oxidation of CH3OH by CrCl2O2
Matrix Isolation Infrared Spectroscopic and Density Functional Study of the Mechanism of the Oxidation of CH3OH by CrCl2O2
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DOI：
10.1021/ja9808752
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发表时间：
1998-06
影响因子：
15
通讯作者：
B. Ault
中科院分区：
文献类型：
--
作者：
B. Ault
基质分离技术已被用来分离几个中间体，在序列中，在CH_3OH的CrCl_2O_2氧化。与以前的理论计算相一致，氢键复合物形成后，最初的双喷射沉积和增强基体退火到33 K。该配合物在波长< 500 nm的汞弧照射下被光破坏，生成HCl和ClCrO 2 OCH 3。这些物种也产生的两个前体在流动系统中的室温反应，然后快速矩阵捕获。将流动反应区加热到150 °C以上导致ClCrO 2 OCH 3的破坏，并产生CH 2 O和HCl。在250 °C以上，由于CH 2 O的谱带被破坏，而由于CO和CO2的谱带生长。进行了高水平密度泛函计算（B3 LYP/6- 311 G *）以确定该体系中的潜在中间体，并提供理论振动光谱以与实验进行比较。
The matrix isolation technique has been employed to isolate several intermediates, in sequence, in the oxidation of CH3OH by CrCl2O2. Consistent with previous theoretical calculations, a hydrogen-bonded complex formed initially after twin jet deposition and was enhanced by matrix annealing to 33 K. This complex was photodestroyed by Hg arc irradiation with λ < 500 nm, and led to the production of HCl and ClCrO2OCH3. These species were also produced by room temperature reaction of the two precursors in a flow system followed by rapid matrix trapping. Heating the flow reaction zone above 150 °C led to destruction of ClCrO2OCH3, and production of CH2O and HCl. Above 250 °C bands due to CH2O were destroyed and bands due to CO and CO2 grew in. High-level density functional calculations (B3LYP/6-311G*) were carried out to identify potential intermediates in this system and to provide theoretical vibrational spectra for comparison to experiment.