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Exploring the Oxidation States of Neptunium with Schiff Base Coordination Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-25 , DOI: 10.1021/acs.inorgchem.0c02455 Bonnie E. Klamm 1, 2 , Cory J. Windorff 1 , Cristian Celis-Barros 1 , Maria J. Beltran-Leiva 1 , Joseph M. Sperling 1 , Thomas E. Albrecht-Schönzart 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-25 , DOI: 10.1021/acs.inorgchem.0c02455 Bonnie E. Klamm 1, 2 , Cory J. Windorff 1 , Cristian Celis-Barros 1 , Maria J. Beltran-Leiva 1 , Joseph M. Sperling 1 , Thomas E. Albrecht-Schönzart 1
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A pair of neptunium Schiff base coordination complexes, NpVIO2L(MeOH) and NpIVL2 {H2L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized and analyzed by several characterization methods including single-crystal X-ray diffraction, electronic absorption, 1H NMR, cyclic voltammetry, and theoretical interpretation. Structural analysis reveals that NpVIO2L(MeOH) and NpIVL2 are isomorphous with the previously reported UVIO2L(MeOH) and MIVL2 (M = Pu, Ce, U, Th) complexes, respectively, allowing for a direct comparison across the series. The reduction of NpVIO2L(MeOH)in situ or direct synthesis from a (NpVO2)+ source shows evidence of a pentavalent neptunyl (NpVO2L)xn– species as determined by UV/vis/NIR and 1H NMR spectroscopy. The synthesis of (NpVO2L)xn– directly from a (NpVO2)+ starting material gives a similar spectrum. Theoretical analysis offers insight into the electronic structure for a better understanding of the bonding patterns and relative stability of the different oxidation states. Computational results show that the Np–L covalent interactions in NpIVL2 are similar to those in the NpVIO2L(MeOH) complex, indicating that neither the presence of the axial oxo ligands nor the oxidation state significantly modify the nature of the Np–L bonds.
中文翻译：
用席夫碱配位化合物探索of的氧化态
一对Sch席夫碱配位化合物Np VI O 2 L（MeOH）和Np IV L 2 { H 2 L = N，N'-双[（4,4'-二乙基氨基）水杨基] -1,2-苯二胺}，已通过几种表征方法合成和分析，包括单晶X射线衍射，电子吸收，1 H NMR，循环伏安法和理论解释。结构分析表明，Np VI O 2 L（MeOH）和Np IV L 2它们分别与先前报道的U VI O 2 L（MeOH）和M IV L 2（M = Pu，Ce，U，Th）配合物同构，从而可以在整个系列中进行直接比较。的还原Np个VI Ô 2 L（甲醇）在原位从（NP或直接合成V Ò 2）+五价neptunyl的源节目证据（NP V Ò 2 L）X ñ -物种如通过UV / VIS测定/ NIR和1 H NMR光谱。的合成（Np V O 2 L）x n –直接来自（Np V O 2）+起始原料，得到相似的光谱。理论分析可深入了解电子结构，以更好地理解键合模式和不同氧化态的相对稳定性。计算结果表明，Np IV L 2中的Np-L共价相互作用与Np VI O 2 L（MeOH）络合物中的相似，表明轴向氧代配体的存在和氧化态都不会显着改变分子的性质。 Np–L键。
更新日期：2020-12-21
中文翻译：
用席夫碱配位化合物探索of的氧化态
一对Sch席夫碱配位化合物Np VI O 2 L（MeOH）和Np IV L 2 { H 2 L = N，N'-双[（4,4'-二乙基氨基）水杨基] -1,2-苯二胺}，已通过几种表征方法合成和分析，包括单晶X射线衍射，电子吸收，1 H NMR，循环伏安法和理论解释。结构分析表明，Np VI O 2 L（MeOH）和Np IV L 2它们分别与先前报道的U VI O 2 L（MeOH）和M IV L 2（M = Pu，Ce，U，Th）配合物同构，从而可以在整个系列中进行直接比较。的还原Np个VI Ô 2 L（甲醇）在原位从（NP或直接合成V Ò 2）+五价neptunyl的源节目证据（NP V Ò 2 L）X ñ -物种如通过UV / VIS测定/ NIR和1 H NMR光谱。的合成（Np V O 2 L）x n –直接来自（Np V O 2）+起始原料，得到相似的光谱。理论分析可深入了解电子结构，以更好地理解键合模式和不同氧化态的相对稳定性。计算结果表明，Np IV L 2中的Np-L共价相互作用与Np VI O 2 L（MeOH）络合物中的相似，表明轴向氧代配体的存在和氧化态都不会显着改变分子的性质。 Np–L键。
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