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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Matrix isolation studies of photochemical and thermal reactions of 3-and 5-membered cyclic hydrocarbons with CrCl2O2
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Matrix isolation studies of photochemical and thermal reactions of 3-and 5-membered cyclic hydrocarbons with CrCl2O2

机译：三元和五元环烃与CrCl2O2的光化学和热反应的基质分离研究

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摘要

The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to characterize the products of the photochemical and thermal reactions of cyclopentadiene, cyclopentene, cyclopentane, and cyclopropane with CrCl2O2. While initial twin jet deposition of the reagents led to no visible changes in the recorded spectra, product bands were observed following irradiation with light of lambda > 300 nm. The irradiation was shown to lead to oxygen atom transfer to the five-membered rings, forming complexes between cyclic alcohol derivatives and CrCl2O. For the cyclopentadiene and cyclopentene systems, complexes between cyclic ketone derivatives and CrCl2O were also observed. For cyclopropane, a ring-opening oxidation reaction followed by fragmentation was observed for the first time, forming the H2C=O-CrCl2O complex and C2H4. In the room temperature thermal (merged jet) reactions between CrCl2O2 and cyclopentadiene, cyclopent-3-enone was observed. At the higher temperatures, 150 and 200 degrees C, 1,3-cyclopentanedione was also observed as well. No product bands were detected in the merged jet experiments for the other three systems. These conclusions were supported by isotopic labeling (H-2) and by B3LYP/6-311G++(d,2p) density functional calculations.
机译：基质分离技术已与红外光谱和理论计算相结合，以表征环戊二烯，环戊烯，环戊烷和环丙烷与CrCl2O2的光化学和热反应产物。虽然试剂的最初双射流沉积导致记录的光谱没有可见变化，但是在用λ> 300 nm的光照射后观察到产物带。结果表明，辐照会导致氧原子转移到五元环上，从而在环状醇衍生物和CrCl2O之间形成络合物。对于环戊二烯和环戊烯体系，还观察到环状酮衍生物与CrCl2O之间的络合物。对于环丙烷，首次观察到开环氧化反应，然后发生断裂，形成H2C = O-CrCl2O络合物和C2H4。在室温下，CrCl2O2与环戊二烯之间发生热（合并射流）反应，观察到环戊-3-烯酮。在较高的温度下（150和200摄氏度），也观察到了1,3-环戊二酮。在其他三个系统的合并喷射实验中未检测到产品带。同位素标记（H-2）和B3LYP / 6-311G ++（d，2p）密度泛函计算支持了这些结论。

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