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≡E (with E = O, S, Se, Te), supported by the (^Ad,MeArOH)₃tacn (1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane) ligand system. Reaction of H₂E with the trivalent precursor [((^Ad,MeArO)₃tacn)U] (1) yields the corresponding uranium(iv) hydrochalcogenido complexes [((^Ad,MeArO)₃tacn)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)][((^Ad,MeArO)₃tacn)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).