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

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,Me ArOH) 3 tacn (1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane) liga...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019-08, Vol.48 (29), p.1853-1864
Main Authors: Rosenzweig, Michael W, Hümmer, Julian, Scheurer, Andreas, Lamsfus, Carlos Alvarez, Heinemann, Frank W, Maron, Laurent, Mazzanti, Marinella, Meyer, Karsten
Format: Article
Language:English
Subjects:
Chemical Physics
Chemical synthesis
Coordination compounds
Crystal structure
Crystallography
Electronic structure
Infrared spectroscopy
Ligands
Magnetic measurement
Molecular structure
Organic chemistry
Physics
Single crystals
Superconducting quantum interference devices
Tellurium
Uranium
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Summary: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,Me ArOH) 3 tacn (1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane) ligand system. Reaction of H 2 E with the trivalent precursor [(( Ad,Me ArO) 3 tacn)U] ( 1 ) yields the corresponding uranium( iv ) hydrochalcogenido complexes [(( Ad,Me ArO) 3 tacn)U(EH)] ( 2 ). Subsequent deprotonation of the terminal hydrochalcogenido species with KN(SiMe 3 ) 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,Me ArO) 3 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). Theoretical and experimental examination of the bonding situation in uranium complexes bearing terminal hydrochalcogenido and chalcogenido ligands.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt00530g