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1 PublicationBonding Trends in Tetravalent Th–Pu Monosalen Complexes
Radoske, T.; März, J.; Patzschke, M.; Kaden, P.; Walter, O.; Schmidt, M.; Stumpf, T.
Abstract
We report the synthesis of three complex series of the form [AnCl₂(salen)(pyx)₂] (H₂salen = N,N’-bis(salicyl¬idene)ethylene-diamine; Pyx = pyridine, 4-methylpyridine, 3,5-dimethylpyridine) with tetravalent early actinides (An = Th, U, Np, Pu) with the goal to elucidate the affinity of these heavy elements for small neutral N-donor molecules. Structure determination via single-crystal XRD and characterization of bulk powders with infrared spectroscopy reveal isostructurality within each respective series and the same complex conformation in all reported structures. While the trend of interatomic distances for An–Cl and An–N (imine nitrogen of salen or pyridyl nitrogen of Pyx) were found to reflect an ionic behaviour, the trend of the An–O distances can only be described with additional covalent interactions for all elements heavier than thorium. All experimental results are supported by quantum chemical calculations, which confirm the mostly ionic character in the An–N and An–Cl bonds, as well as the highest degree of covalency of the An–O bonds. Structurally, the calculations indicate just minor electronic or steric effects of the additional Pyx substituents on the complex properties.
Keywords: tetravalent actinide; salen; covalency; pyridine; bonding analysis; thorium; uranium; neptunium; plutonium
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Data for: Bonding Trends in Tetravalent Th–Pu Monosalen Complexes
ROBIS: 31730 HZDR-primary research data are used by this (Id 31714) publication
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Chemistry - A European Journal 26(2020)70, 16853-16859
DOI: 10.1002/chem.202003241
Cited 10 times in Scopus
Permalink: https://www.hzdr.de/publications/Publ-31714