Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan.
J Chem Phys. 2012 Mar 28;136(12):124510. doi: 10.1063/1.3696894.
Irradiation at 239 ± 20 nm of a p-H(2) matrix containing methoxysulfinyl chloride, CH(3)OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν(1), CH(2) antisymmetric stretching), 2999.5 (ν(2), CH(3) antisymmetric stretching), 2950.4 (ν(3), CH(3) symmetric stretching), 1465.2 (ν(4), CH(2) scissoring), 1452.0 (ν(5), CH(3) deformation), 1417.8 (ν(6), CH(3) umbrella), 1165.2 (ν(7), CH(3) wagging), 1152.1 (ν(8), S=O stretching mixed with CH(3) rocking), 1147.8 (ν(9), S=O stretching mixed with CH(3) wagging), 989.7 (ν(10), C-O stretching), and 714.5 cm(-1) (ν(11), S-O stretching) modes of syn-CH(3)OSO. When CD(3)OS(O)Cl in a p-H(2) matrix was used, lines at 2275.9 (ν(1)), 2251.9 (ν(2)), 2083.3 (ν(3)), 1070.3 (ν(4)), 1056.0 (ν(5)), 1085.5 (ν(6)), 1159.7 (ν(7)), 920.1 (ν(8)), 889.0 (ν(9)), 976.9 (ν(10)), and 688.9 (ν(11)) cm(-1) appeared and are assigned to syn-CD(3)OSO; the mode numbers correspond to those used for syn-CH(3)OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86∕aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH(3)OSO near 2991, 2956, 1152, and 994 cm(-1) to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD(3)OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H(2) such that the Cl atom, produced via UV photodissociation of CH(3)OS(O)Cl in situ, might escape from the original cage to yield isolated CH(3)OSO radicals.
在 3.2 K 下，用中压汞灯过滤后的光辐照含有甲氧基磺酰氯（CH3OS(O)Cl）的 p-H2基质，在 239 ± 20 nm 处产生红外（IR）吸收线，位于 3028.4（归因于 ν1，CH2反对称伸缩）、2999.5（ν2，CH3反对称伸缩）、2950.4（ν3，CH3对称伸缩）、1465.2（ν4，CH2剪式）、1452.0（ν5，CH3变形）、1417.8（ν6，CH3伞状）、1165.2（ν7，CH3摆动）、1152.1（ν8，S=O 伸缩混合 CH3摇摆）、1147.8（ν9，S=O 伸缩混合 CH3摆动）、989.7（ν10，C-O 伸缩）和 714.5 cm-1（ν11，S-O 伸缩）模式的 syn-CH3OSO。当 p-H2基质中使用 CD3OS(O)Cl 时，出现了 2275.9（ν1）、2251.9（ν2）、2083.3（ν3）、1070.3（ν4）、1056.0（ν5）、1085.5（ν6）、1159.7（ν7）、920.1（ν8）、889.0（ν9）、976.9（ν10）和 688.9（ν11）cm-1的线，这些线归因于 syn-CD3OSO；模式编号对应于用于 syn-CH3OSO 的编号。这些分配是基于光解行为以及观察到的振动波数、红外强度和氘同位素位移与用 B3P86∕aug-cc-pVTZ 方法预测的结果进行比较得出的。我们的结果将先前报道的气态 syn-CH3OSO 附近的四个瞬态红外吸收带（2991、2956、1152 和 994 cm-1）扩展到 11 条线，包括与 C-O、O-S 和 S=O 伸缩模式相关的线。syn-CD3OSO 的振动波数是新的。这些结果表明了固态 p-H2减小笼效应的优势，使得通过原位 UV 光解 CH3OS(O)Cl 产生的 Cl 原子可能从原始笼中逸出，从而产生孤立的 CH3OSO 自由基。
