Formation of reduced species from dichlorobis(pentamethylcyclopentadienyl)uranium(IV), dichlorobis(pentamethylcyclopentadienyl)thorium(IV), chloro(pentamethylcyclopentadienyl)magnesium(II), and chloroisopropylmagnesium(II) by pulse radiolysis of their solutions in tetrahydrofuran
Formation of reduced species from dichlorobis(pentamethylcyclopentadienyl)uranium(IV), dichlorobis(pentamethylcyclopentadienyl)thorium(IV), chloro(pentamethylcyclopentadienyl)magnesium(II), and chloroisopropylmagnesium(II) by pulse radiolysis of their solutions in tetrahydrofuran
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通过脉冲辐射分解二氯双（五甲基环戊二烯基）铀（IV）、二氯双（五甲基环戊二烯基）钍（IV）、氯（五甲基环戊二烯基）镁（II）和氯异丙基镁（II）在四氢呋喃中的溶液形成还原物质
DOI：
10.1021/ic00266a021
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发表时间：
1987
影响因子：
4.6
通讯作者：
G. Folcher
中科院分区：
文献类型：
--
作者：
A. Koulkes;J. Marechal;A. Dormond;G. Folcher
利用脉冲辐射分解技术，化合物（C5Me5） 2ThCl2被四氢呋喃（THF）溶液中产生的溶剂化电子（e'THF）还原。过渡种的电子光谱归因于钍（III）配合物。这些结果与电化学结果一致；在实验条件下，钍（IV）在2.32 ~ 2.8 V （vs. SCE）范围内还原为钍（III）。e~ THF与配合物（C5Me5） 2UCl2、（C5Me5） MgCl、-PrMgCl和ZnCl2相互作用，分别生成铀（III）、镁(I)和锌(I)。建立了电子谱、消失率和反应顺序。（C5Me5） 2UCl2、（C5Me5） 2ThCl2、（C5Me;） MgCl和/-PrMgCl的还原速率常数分别为（1.2±0.1）X 10”、（4.4±0.1）X 109、（2.9±0.05）X 109和（0.7±0.1）X 109 M”1s’1。
By use of the pulse radiolysis technique, the compound (C5Me5) 2ThCl2 has been reduced by the solvated electrons (e'THF) created in tetrahydrofuran (THF) solution. The electronic spectrum of the transition specieswas attributed to a thorium (III) complex. These results are consistent with those obtained by electrochemistry; the reduction of thorium (IV) to thorium (III) occurred in the 2.32-2.8 V (vs. SCE) range under the experimental conditions. The interaction of e~ THF with the complexes (C5Me5) 2UCl2,(C5Me5) MgCl,-PrMgCl, and ZnCl2 led to uranium (III), magnesium (I), and Zn (I) species, respectively. Electronic spectra, disappearance rates, and the reaction order were established. The rate constants of reductions of (C5Me5) 2UCl2,(C5Me5) 2ThCl2,(C5Me;) MgCl, and/-PrMgCl are (1.2±0.1) X 10",(4.4±0.1) x 109,(2.9±0.05) X 109, and (0.7±0.1) X 109 M" 1 s'1, respectively.