Generation and characterization of a distonic biradical anion formed from an enediynone prodrug in the gas phase.
Generation and characterization of a distonic biradical anion formed from an enediynone prodrug in the gas phase.
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DOI：
10.1007/s13361-012-0567-8
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发表时间：
2013-04
影响因子：
3.2
通讯作者：
Kenttaemaa, Hilkka I.
中科院分区：
文献类型：
--
作者：
Yang, Linan;Bekele, Tefsit;Lipton, Mark A.;Kenttaemaa, Hilkka I.
关键词：
通过去质子化的双环[8.3.0]十三碳-12-烯-2，7-二炔-1-酮前体的环化，在气相中成功地产生了带负电荷的双自由基中间体。这种双自由基的固有负电荷允许其通过碰撞激活解离以及在FT-ICR质谱仪中与各种中性底物的反应进行表征。虽然双自由基对通常与带正电荷的双自由基快速反应的试剂（如二甲基二硫醚）不反应，但它通过溴或氯原子夺取与含卤素的底物四氯化碳、四溴化碳和溴三氯甲烷反应，这支持了其双自由基结构。在这项研究中提出的结果表明，环化通常用于在溶液中形成双自由基中间体从烯二炔化合物也可能发生在气相中。
A negatively charged biradical intermediate was successfully generated in the gas phase via cyclization of the deprotonated bicyclo[8.3.0]trideca-12-ene-2,7-diyn-1-one precursor. The inherent negative charge of this biradical allows its characterization via collision-activated dissociation and reactions with a variety of neutral substrates in an FT-ICR mass spectrometer. Although the biradical is unreactive toward reagents that usually react rapidly with positively charged biradicals, such as dimethyl disulfide, it reacts with the halogen-containing substrates carbon tetrachloride, carbon tetrabromide and bromotrichloromethane via bromine or chlorine atom abstraction, which supports its biradical structure. The results presented in this study indicate that cyclizations commonly used in solution to form biradical intermediates from enediyne compounds may also occur in the gas phase.
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影响因子：
7.4
作者：
CHEN, L;WANG, TCL;MARSHALL, AG
通讯作者：
MARSHALL, AG
影响因子：
15
作者：
Amegayibor, FS;Nash, JJ;Kenttämaa, HI
通讯作者：
Kenttämaa, HI
影响因子：
16.6
作者：
Jankiewicz, Bartlomiej J.;Reece, Jennifer N.;Kenttamaa, Hilkka I.
通讯作者：
Kenttamaa, Hilkka I.
影响因子：
16.6
作者：
Jankiewicz, Bartlomiej J.;Adeuya, Anthony;Kenttaemaa, Hilkka I.
通讯作者：
Kenttaemaa, Hilkka I.
影响因子：
6.2
作者：
GAUTHIER, JW;TRAUTMAN, TR;JACOBSON, DB
通讯作者：
JACOBSON, DB