Formation and hydrolysis of gas-phase [UO 2 (R)] + : R═CH 3 , CH 2 CH 3 , CH═CH 2 , and C 6 H 5
Formation and hydrolysis of gas-phase [UO 2 (R)] + : R═CH 3 , CH 2 CH 3 , CH═CH 2 , and C 6 H 5
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气相[UO 2 (R)]的形成和水解：R→CH 3 、CH 2 CH 3 、CH→CH 2 和C 6 H 5
DOI：
10.1002/jms.4430
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发表时间：
2019
影响因子：
2.3
通讯作者：
Van Stipdonk, Michael
中科院分区：
文献类型：
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作者：
Tatosian, Irena;Bubas, Amanda;Iacovino, Anna;Kline, Susan;Metzler, Luke;Van Stipdonk, Michael
本研究的目标是：（a）通过[UO 2（O2 C ─R）]+前体的脱羧作用产生通式为[UO 2（R）]+的带正电荷的有机铀酰络合物（例如，R = CH 3和CH 2 CH 3）;（B）确定络合物（如果形成）通过碰撞活化解离或在暴露于气相H2 O时发生反应的途径。[UO 2（O2 C-CH 3）]+和[UO 2（O2 C-CH 2CH 3）]+的碰撞诱导解离（CID）导致H+转移和乙烯酮消除，留下[UO 2（OH）]+。而醇盐[UO_2（OCH_2CH_3）]~+和[UO_2（OCH_2CH_2CH_3）]~+的CID分别生成[UO_2（CH_3）]~+和[UO_2（CH_2CH_3）]~+。分离[UO 2（CH 3）]+和[UO 2（CH 2CH 3）]+与H2O反应，通过消除·CH 3和·CH 2CH 3形成[UO 2（H2O）]+：未观察到水解。络合物的丙烯酸酯和苯甲酸酯形式[UO 2（O2 C ─CH <$CH 2）]+和[UO 2（O2 C ─ C6 H 5）]+的CID分别引起脱羧，留下[UO 2（CH <$CH 2）]+和[UO 2（C6 H 5）]+。这些有机金属物质与H2O反应生成[UO 2（OH）]+，并且没有检测到相应的自由基损失而留下[UO 2（H2O）]+。密度泛函理论计算表明，形成[UO 2（OH）]+，而不是水合UVO 2+，阳离子是积极的青睐，无论前体离子。然而，对于[UO 2（CH 3）]+和[UO 2（CH 2CH 3）]+前体，质子转移生成[UO 2（OH）]+和相关中性烷烃的过渡态能量高于涉及直接消除有机中性形成[UO 2（H2O）]+的路径。[UO 2（CH <$CH2）]+和[UO 2（C6 H5）]+前体的情况相反：质子转移的过渡态低于通过消除CH <$CH2或C6 H5自由基产生[UO 2（H2O）]+所需的能量。
The goals of the present study were (a) to create positively charged organo‐uranyl complexes with general formula [UO2(R)]+(eg, R═CH3and CH2CH3) by decarboxylation of [UO2(O2C─R)]+precursors and (b) to identify the pathways by which the complexes, if formed, dissociate by collisional activation or otherwise react when exposed to gas‐phase H2O. Collision‐induced dissociation (CID) of both [UO2(O2C─CH3)]+and [UO2(O2C─CH2CH3)]+causes H+transfer and elimination of a ketene to leave [UO2(OH)]+. However, CID of the alkoxides [UO2(OCH2CH3)]+and [UO2(OCH2CH2CH3)]+produced [UO2(CH3)]+and [UO2(CH2CH3)]+, respectively. Isolation of [UO2(CH3)]+and [UO2(CH2CH3)]+for reaction with H2O caused formation of [UO2(H2O)]+by elimination of ·CH3and ·CH2CH3: Hydrolysis was not observed. CID of the acrylate and benzoate versions of the complexes, [UO2(O2C─CH═CH2)]+and [UO2(O2C─C6H5)]+, caused decarboxylation to leave [UO2(CH═CH2)]+and [UO2(C6H5)]+, respectively. These organometallic species do react with H2O to produce [UO2(OH)]+, and loss of the respective radicals to leave [UO2(H2O)]+was not detected. Density functional theory calculations suggest that formation of [UO2(OH)]+, rather than the hydrated UVO2+, cation is energetically favored regardless of the precursor ion. However, for the [UO2(CH3)]+and [UO2(CH2CH3)]+precursors, the transition state energy for proton transfer to generate [UO2(OH)]+and the associated neutral alkanes is higher than the path involving direct elimination of the organic neutral to form [UO2(H2O)]+. The situation is reversed for the [UO2(CH═CH2)]+and [UO2(C6H5)]+precursors: The transition state for proton transfer is lower than the energy required for creation of [UO2(H2O)]+by elimination of CH═CH2or C6H5radical.