Observation and characterization of the CH3S(O)CH- and CH3S(O)CH- x H2O carbene anions by photoelectron imaging and photofragment spectroscopy.
Observation and characterization of the CH3S(O)CH- and CH3S(O)CH- x H2O carbene anions by photoelectron imaging and photofragment spectroscopy.
复制标题
通过光电子成像和光碎片光谱观察和表征 CH3S(O)CH- 和 CH3S(O)CH- x H2O 卡宾阴离子。
DOI：
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发表时间：
2009
影响因子：
2.9
通讯作者：
A. Sanov
中科院分区：
文献类型：
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作者：
L. Velarde;T. Habteyes;R. Glass;A. Sanov
我们报道了CH(3)S(O)CH（-）和CH(3)S(O)CH(-) x H(2)O碳阴离子在O（-）从二甲亚砜中整体提取H(2)（+）后形成的观察结果。光电子能谱揭示了剩余中性的单线态和三重态碳，单线态被指定为基态。虽然也预计会形成一些双离子CH(2)S(O)CH(2)（-）自由基阴离子，但没有发现这种异构体存在的确凿证据。HCSO（-）的光电子能谱也是首次报道。在532 nm光下对CH(3)S(O)CH（-）进行光破碎，发现两种主要的阴离子产物：甲基消除产生的HCSO（-）片段和较弱的SO（-）产物。对于一水合阴离子，观察到额外的SO(-) x H(2)O片段。有趣的是，与裸CH(3)S(O)CH（-）阴离子解离的SO（-）产率相比，在CH(3)S(O)CH（-）的裂解过程中，SO(-) x H(2)O和SO（-）产物的产率都要高得多。提出了两种可能的途径作为基于SO（-）的光产物的可能机制，它们都涉及光诱导的分子内重排和C-C键的形成。
We report the observation of the CH(3)S(O)CH(-) and CH(3)S(O)CH(-) x H(2)O carbene anions formed upon overall H(2)(+) abstraction from dimethyl sulfoxide by O(-). Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH(2)S(O)CH(2)(-) radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO(-) is also reported for the first time. Photofragmentation of CH(3)S(O)CH(-) with 532 nm light reveals two main types of anionic products: a dominant HCSO(-) fragment, resulting from methyl elimination, and a less intense SO(-) product. For the monohydrated anion, an additional SO(-) x H(2)O fragment is observed. Intriguingly, both the SO(-) x H(2)O and SO(-) products are produced with much higher yields in the fragmentation of CH(3)S(O)CH(-) x H(2)O, compared to the SO(-) yield from the dissociation of the bare CH(3)S(O)CH(-) anion. Two possible pathways are proposed as likely mechanisms for the SO(-)-based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.