Rosenzweig Michael W, Hümmer Julian, Scheurer Andreas, Lamsfus Carlos Alvarez, Heinemann Frank W, Maron Laurent, Mazzanti Marinella, Meyer Karsten
Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany.
LPCNO, Université de Toulouse, INSA Toulouse, 135 Avenue de Rangueil, 31077 Toulouse, France.
Dalton Trans. 2019 Aug 7;48(29):10853-10864. doi: 10.1039/c9dt00530g. Epub 2019 Apr 5.
We here report the synthesis and characterization of a complete series of terminal hydrochalcogenido, U-EH, and chalcogenido uranium(iv) complexes, U≡E (with E = O, S, Se, Te), supported by the (ArOH)tacn (1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane) ligand system. Reaction of HE with the trivalent precursor [((ArO)tacn)U] (1) yields the corresponding uranium(iv) hydrochalcogenido complexes [((ArO)tacn)U(EH)] (2). Subsequent deprotonation of the terminal hydrochalcogenido species with KN(SiMe), in the presence of 2.2.2-cryptand, gives access to the uranium(iv) complexes with terminal chalcogenido ligands [K(2.2.2-crypt)][((ArO)tacn)U≡E] (3). In order to study the influence of the varying terminal chalogenido ligands on the overall molecular and electronic structure, all complexes were studied by single-crystal X-ray diffractometry, UV/vis/NIR, electronic absorption, and IR vibrational spectroscopy as well as SQUID magnetometry and computational analyses (DFT, MO, NBO).
我们在此报告了一系列由（ArOH）tacn（1,4,7-三（3-（1-金刚烷基）-5-甲基-2-羟基苄基）-1,4,7-三氮杂环壬烷）配体体系支撑的末端氢硫属化物、U-EH和硫属化物铀（IV）配合物U≡E（其中E = O、S、Se、Te）的合成与表征。HE与三价前体[((ArO)tacn)U]（1）反应生成相应的铀（IV）氢硫属化物配合物[((ArO)tacn)U(EH)]（2）。随后，在2.2.2-穴醚存在下，用KN(SiMe)对末端氢硫属化物物种进行去质子化，得到具有末端硫属化物配体的铀（IV）配合物[K(2.2.2-crypt)][((ArO)tacn)U≡E]（3）。为了研究不同末端硫属化物配体对整体分子和电子结构的影响，通过单晶X射线衍射、紫外/可见/近红外、电子吸收和红外振动光谱以及超导量子干涉仪磁力测定和计算分析（密度泛函理论、分子轨道、自然键轨道）对所有配合物进行了研究。
