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首页> 外文期刊>Chemistry: A European journal >Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis-N2O2·O2 complex and of sym-N2O4 in Solid Ne Matrices
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Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis-N2O2·O2 complex and of sym-N2O4 in Solid Ne Matrices

机译：涉及一氧化氮氧化的中间体：固态Ne矩阵中顺式-N2O2·O2络合物和sym-N2O4的光化学

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摘要

Pure sym-N2O4 isolated in solid Ne was obtained by passing cold neon gas over solid N2O4 at 115 8C and quenching the resulting gaseous mixture at 6.3 K. Filtered UV irradiation (260–400 nm) converts sym-N2O4 into trans-ONONO2, a weakly interacting (NO2)2 radical pair, and traces of the cis-N2O2·O2 complex. Besides the weakly bound ON·O2 complex, cis- N2O2·O2 was also obtained by co-deposition of NO and O2 in solid Ne at 6.3 K, and both complexes were characterised by their matrix IR spectra. Concomitantly formed cis-N2O2 dissociated on exposure to filtered IR irradiation (400–8000 cm1), and the cis- N2O2·O2 complex rearranged to sym- N2O4 and trans-ONONO2. Experiments using 18O2 in place of 16O2 revealed a non-concerted conversion of cis- N2O2·O2 into these species, and gave access to four selectively di-18O-substituted trans-ONONO2 isotopomers. No isotopic scrambling occurred. The IR spectra of sym-N2O4 and of trans-ONONO2 in solid Ne were recorded.IR fundamentals of trans-ONONO2 were assigned based on experimental 16/18O isotopic shifts and guided by DFT calculations. Previously reported contradictory measurements on cisand trans-ONONO2 are discussed. Dinitroso peroxide, ONOONO, a proposed intermediate in the IR photoinduced rearrangement of cis-N2O2·O2 to the various N2O4 species, was not detected.Its absence in the photolysis products indicates a low barrier(10 kJmol1) for its exothermic OO bond homolysis into a (NO2)2 radicalpair.
机译：通过在115 8C下使冷氖气流过固体N2O4并在6.3 K处淬灭生成的气态混合物，获得分离出的固体Ne中的纯sym-N2O4。经过过滤的紫外线照射（260-400 nm）将sym-N2O4转化为反式ONONO2弱相互作用的（NO2）2自由基对和顺式-N2O2·O2络合物的痕迹。除了弱键合的ON·O2配合物外，还通过在6.3 K的固体Ne中共沉积NO和O2获得了顺式N2O2·O2，并且两种配合物的特征在于其基体红外光谱。伴随形成的顺式-N2O2在暴露于过滤的红外辐射（400-8000 cm1）时解离，顺式-N2O2·O2络合物重排为对称-N2O4和反式-ONONO2。使用18O2代替16O2进行的实验表明，未经证实的是将顺式N2O2·O2转化为这些物种，并获得了四个选择性的被18-18取代的反式ONONO2异构体。没有发生同位素加扰。记录了固态Ne中sym-N2O4和反式ONONO2的红外光谱。基于实验的16 / 18O同位素位移并通过DFT计算指导了反式ONONO2的红外光谱基础。讨论了先前报道的对顺式和反式ONONO2的矛盾测量。未检测到过氧化亚硝基二氧化物ONOONO，该中间体在红外光诱导的顺式-N2O2·O2到各种N2O4物种的重排过程中被发现，在光解产物中不存在表明其放热的OO键均化为低阻隔（10 kJmol1）。 （NO2）2自由基对。

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