关于铀（IV）酰胺和铀（V）亚胺配合物电子结构的见解。
Insights into the Electronic Structure of a U(IV) Amido and U(V) Imido Complex.
作者信息
Köhler Luisa, Patzschke Michael, Bauters Stephen, Vitova Tonya, Butorin Sergei M, Kvashnina Kristina O, Schmidt Moritz, Stumpf Thorsten, März Juliane
机构信息
Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Bautzner Landstraße 400, 01328, Dresden, Germany.
The Rossendorf Beamline at ESRF at the European Synchrotron, CS40220, 38043, Grenoble Cedex 9, France.
出版信息
Chemistry. 2022 Apr 12;28(21):e202200119. doi: 10.1002/chem.202200119. Epub 2022 Mar 14.
Reaction of the N-heterocylic carbene ligand PrIm (L ) and lithium bis(trimethylsilyl)amide (TMSA) as a base with UCl resulted in U(IV) and U(V) complexes. Uranium's +V oxidation state in (HL ) [U(V)(TMSI)Cl ] (TMSI=trimethylsilylimido) (2) was confirmed by HERFD-XANES measurements. Solid state characterization by SC-XRD and geometry optimisation of [U(IV)(L ) (TMSA)Cl ] (1) indicated a silylamido ligand mediated inverse trans influence (ITI). The ITI was examined regarding different metal oxidation states and was compared to transition metal analogues by theoretical calculations.
氮杂环卡宾配体PrIm（L）与作为碱的双（三甲基硅基）氨基锂（TMSA）与UCl反应生成了U（IV）和U（V）配合物。通过高能量分辨率荧光X射线吸收近边结构（HERFD-XANES）测量证实了（HL）[U（V）（TMSI）Cl]（TMSI = 三甲基硅基亚氨基）（2）中铀的+V氧化态。通过单晶X射线衍射（SC-XRD）进行的固态表征以及[U（IV）（L）（TMSA）Cl]（1）的几何优化表明了硅基酰胺配体介导的反位影响（ITI）。针对不同的金属氧化态研究了这种反位影响，并通过理论计算将其与过渡金属类似物进行了比较。
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