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Updated: Mar 7, 2026
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Molecular and Electronic Structures of Eight-Coordinate Uranium Bipyridine Complexes: A Rare Example of a Bipy2-
Michael W Rosenzweig1, Frank W Heinemann1, Laurent Maron2
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University Erlangen-Nürnberg (FAU) , Egerlandstrasse 1, 91058 Erlangen, Germany.
Abstract:
Reaction of trivalent [((Ad,tBuArO)3tacn)U] (1) with 2,2'-bipyridine (bipy) yields [((Ad,tBuArO)3tacn)U(bipy)] (2) and subsequent reduction of 2 with KC8 in the presence of Kryptofix222 furnishes [K(2.2.2-crypt)][((Ad,tBuArO)3tacn)U(bipy)] (3). Alternatively, complex 3 can be synthesized from 1 by addition of [K(bipy)] in the presence of the cryptand. New complexes 2 and 3 are characterized by a variety of spectroscopic, electrochemical, and magnetochemical methods, single-crystal X-ray diffraction, computational methods, and CHN elemental analysis. Structural analyses reveal a bipyridine radical (bipy•-) ligand in 2 and a dianionic (bipy2-) species in 3. Complex 3 represents a rare example of an isolated and unambiguously characterized bipy2- ligand coordinated to a uranium ion. The electronic structure assignments are supported by UV/vis/NIR and EPR spectroscopy, as well as SQUID magnetometry. The results of CASSCF calculations indicate multiconfigurational ground states for complexes 2 and 3. The electronic ground state for 2 consists of an open-shell doublet U4+(bipy•-) state (91%) and a closed-shell doublet U5+(bipy2-) state (9%). The almost degenerate multiconfigurational ground state for 3 was found to be composed of an open-shell singlet and pure triplet state 0.06 eV higher in energy, both resulting from the U4+(5f2) (bipy2-) configuration.
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