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A Comparative IRMPD and DFT Study of Fe3+ and UO22+ Complexation with N-Methylacetohydroxamic Acid
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02567 Thibault Terencio 1 , Jana Roithová 1 , Stéphane Brandès 2 , Yoann Rousselin 2 , Marie-José Penouilh 2 , Michel Meyer 2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02567 Thibault Terencio 1 , Jana Roithová 1 , Stéphane Brandès 2 , Yoann Rousselin 2 , Marie-José Penouilh 2 , Michel Meyer 2
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Iron(III) and uranyl complexes of N-methylacetohydroxamic acid (NMAH) have been investigated by mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. A comparison between IRMPD and theoretical IR spectra enabled one to probe the structures for some selected complexes detected in the gas phase. The results show that coordination of Fe3+ and UO22+ by hydroxamic acid is of a very similar nature. Natural bond orbital analysis suggests that bonding in uranyl complexes possesses a slightly stronger ionic character than that in iron complexes. Collision-induced dissociation (CID), IRMPD, and 18O-labeling experiments unambiguously revealed a rare example of the U═O bond activation concomitant with the elimination of a water molecule from the gaseous [UO2(NMA)(NMAH)2]+ complex. The U═O bond activation is observed only for complexes with one monodentate NMAH molecule forming a hydrogen bond toward one “yl” oxygen atom, as was found by DFT calculations. This reactivity might explain oxygen exchange observed for uranyl complexes.
中文翻译：
Fe 3+和UO 2 2+与N-甲基乙酰氧肟酸络合的IRMPD和DFT对比研究
已通过质谱，红外多光子离解（IRMPD）光谱和密度泛函理论（DFT）计算研究了N-甲基乙酰氧肟酸（NMAH）的铁（III）和铀酰配合物。IRMPD与理论IR光谱之间的比较使人们能够探测气相中检测到的某些选定配合物的结构。结果表明异羟肟酸对Fe 3+和UO 2 2+的配位具有非常相似的性质。自然键轨道分析表明，与铁配合物相比，铀酰配合物中的结合具有稍强的离子特性。碰撞诱导解离（CID），IRMPD和18O标记实验清楚地揭示了U═O键活化的罕见例子，同时从气态[UO 2（NMA）（NMAH）2 ] +络合物中消除了水分子。DFT计算发现，只有在一个单齿NMAH分子朝一个“ yl”氧原子形成氢键的配合物中，才能观察到U═O键的活化。这种反应性可能解释了对于铀酰复合物观察到的氧交换。
更新日期：2018-01-16
中文翻译：
Fe 3+和UO 2 2+与N-甲基乙酰氧肟酸络合的IRMPD和DFT对比研究
已通过质谱，红外多光子离解（IRMPD）光谱和密度泛函理论（DFT）计算研究了N-甲基乙酰氧肟酸（NMAH）的铁（III）和铀酰配合物。IRMPD与理论IR光谱之间的比较使人们能够探测气相中检测到的某些选定配合物的结构。结果表明异羟肟酸对Fe 3+和UO 2 2+的配位具有非常相似的性质。自然键轨道分析表明，与铁配合物相比，铀酰配合物中的结合具有稍强的离子特性。碰撞诱导解离（CID），IRMPD和18O标记实验清楚地揭示了U═O键活化的罕见例子，同时从气态[UO 2（NMA）（NMAH）2 ] +络合物中消除了水分子。DFT计算发现，只有在一个单齿NMAH分子朝一个“ yl”氧原子形成氢键的配合物中，才能观察到U═O键的活化。这种反应性可能解释了对于铀酰复合物观察到的氧交换。
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