A complete series of uranium(iv) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Dalton Transactions Year : 2019

A complete series of uranium(iv) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te

Abstract

We here report the synthesis and characterization of a complete series of terminal hydrochalcogenido, U-EH, and chalcogenido uranium(iv) complexes, U equivalent to E (with E = O, S, Se, Te), supported by the ((ArOH)-Ar-Ad,Me)(3)tacn (1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane) ligand system. Reaction of H2E with the trivalent precursor [(((ArO)-Ar-Ad,Me)(3)tacn)U] (1) yields the corresponding uranium(iv) hydrochalcogenido complexes [(((ArO)-Ar-Ad,Me)(3)tacn)U(EH)] (2). Subsequent deprotonation of the terminal hydrochalcogenido species with KN(SiMe3)(2), 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)-Ar-Ad,Me)(3)tacn)U equivalent to 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).

Dates and versions

hal-04022174 , version 1 (09-03-2023)

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Michael W. Rosenzweig, Julian Huemmer, Andreas Scheurer, Carlos Alvarez Lamsfus, Frank W. Heinemann, et al.. A complete series of uranium(iv) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te. Dalton Transactions, 2019, 48 (29), pp.10853-10864. ⟨10.1039/c9dt00530g⟩. ⟨hal-04022174⟩
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