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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Formation of Cyanate (OCN) and Fulminate (ONC) Radicals from Anionic Precursors in the Gas Phase. A Joint Experimental and Theoretical Study
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Formation of Cyanate (OCN) and Fulminate (ONC) Radicals from Anionic Precursors in the Gas Phase. A Joint Experimental and Theoretical Study

机译：在气相中由阴离子前体形成氰酸根（OCN）和氟根（ONC）自由基。联合实验和理论研究

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摘要

The cyanate anion (OCN)~- amy be formed in the ion source of a reverse sector VG ZAB 2HF mass spectrometer by dissociative electron capture of phenyl cyanate (PhOCN). The isomeric fulminate anion (ONC) is formed by (i) deprotonation of nitromethane (with HO~-) followed by elimination of H_2O (-CH_2NO_2 → [(CHN(O)(OH)]~- → (ONC)~- + H_2O) and (ii) the reaction between CH_2 = N - OCH_3 and O~(·-) [CH_2 = N - OCH_3 + O~(·-) → (ONC)~- + H_2O +CH_3~·]. Neutralization of the cyanate and fulminate anions by Franck-Condon vertical one-electron oxidation (in the first of two tandem collision cells of the mass spectrometer) yields the cyanate (OCN) and fulminate (ONC) radicals, both of which are stable for at least 1 μs. Ionization of these neutrals by one-electron oxidation in a second collision cell produces the cyanate and fulminate cations. A proportion of each of these cations undergoes isomerization. Theoretical and experimental studies show that (i) these rearrangements involve the less stable single forms of the cations, (ii) the cationic fulminate to cyanate rearrangement is a major process, and (iii) the corresponding rearrangement of the cyanate cation is a minor process, with the product being either the oxazirinyl cation or the fulminate cation.
机译：氰酸根阴离子（OCN）-可通过离解性电子捕获氰酸苯酯（PhOCN）的方式在反向扇区VG ZAB 2HF质谱仪的离子源中形成。通过（i）硝基甲烷去质子化（用HO〜-）然后消除H_2O（-CH_2NO_2→[（CHN（O）（OH）]〜-→（ONC）〜-+ H_2O）和（ii）CH_2 = N-OCH_3与O〜（·-）[CH_2 = N-OCH_3 + O〜（·-）→（ONC）〜-+ H_2O + CH_3〜·]之间的反应。通过Franck-Condon垂直单电子氧化法（在质谱仪的两个串联碰撞池中的第一个）中的氰酸根和富铝酸根阴离子产生氰酸根（OCN）和富铝酸根（ONC）自由基，两者均稳定至少1 μs。在第二个碰撞池中通过单电子氧化将这些中性离子电离，生成氰酸盐和黄酸盐阳离子，每种阳离子中的一部分进行异构化，理论和实验研究表明（i）这些重排涉及稳定性较差的单一形式在阳离子中，（ii）阳离子黄酸盐化成氰酸酯的重排是一个主要过程，并且（iii）相应的氰酸酯重排阳离子是一个次要的过程，产物是恶二嗪基阳离子或黄体阳离子。

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