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

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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).

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

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Publication details

The article was received on 02 Feb 2019, accepted on 25 Mar 2019 and first published on 25 Mar 2019


Article type: Paper
DOI: 10.1039/C9DT00530G
Dalton Trans., 2019, Advance Article

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

    M. W. Rosenzweig, J. Hümmer, A. Scheurer, C. A. Lamsfus, F. W. Heinemann, L. Maron, M. Mazzanti and K. Meyer, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT00530G

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