Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487, United States.
Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16C, 106 91 Stockholm, Sweden.
Inorg Chem. 2020 Mar 2;59(5):2861-2869. doi: 10.1021/acs.inorgchem.9b03228. Epub 2020 Feb 10.
We investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (CCImT) with Nd(NO)·6HO and UOCl·3HO led to the isolation of the anhydrous thione complexes Nd(NO)(CCImT) and UOCl(CCImT), characterized by single crystal X-ray diffraction. Differences in the strength of metal-thione interactions have been examined by means of the crystal structure analysis and density functional theory (DFT) calculations. The CCImT ligands were found to be affected by both coordination and noncovalent interactions, making it impossible to deconvolute the effects of one from the other. Calculated partial atomic charges indicated greater ligand-to-metal charge transfer in the [UO] complex, indicative of a stronger interaction. The reactivity of CCImT demonstrates its usefulness in the preparation of f-element soft donor complexes from readily available hydrates that could be useful intermediates for promoting the coordination and studying the effects of soft donor anions.
我们研究了相对路易斯碱性的咪唑-2-硫酮是否可以替代与 f 族阳离子结合的水分子配体，并生成 f 族软给体配合物。1,3-二乙基咪唑-2-硫酮（CCImT）与 Nd(NO)·6H₂O 和 UOCl·3H₂O 的反应导致了无水硫酮配合物 Nd(NO)(CCImT)和 UOCl(CCImT)的分离，其结构通过单晶 X 射线衍射进行了表征。通过晶体结构分析和密度泛函理论（DFT）计算研究了金属-硫酮相互作用的强度差异。CCImT 配体受到配位和非共价相互作用的双重影响，使得无法将一种作用从另一种作用中分离出来。计算得到的部分原子电荷表明，[UO]配合物中配体到金属的电荷转移更大，表明相互作用更强。CCImT 的反应性表明它可用于从易得的水合物制备 f 族软给体配合物，这些配合物可能是促进配位和研究软给体阴离子影响的有用中间体。
