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Updated: Sep 24, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis and Reduction of Heteroleptic Bis(cyclopentadienyl) Uranium(III) Complexes
Justin C Wedal1, Joseph W Ziller1, Filipp Furche1
1Department of Chemistry, University of California Irvine, Irvine, California 92697, United States.
Abstract:
Heteroleptic U(III) complexes supported by bis(cyclopentadienyl) frameworks have been synthesized to examine their suitability as precursors to U(II) complexes. The newly synthesized (C5Me5)2U(OC6H2tBu2-2,6-Me-4), (C5Me5)2U(OC6H2Ad2-2,6-tBu-4) (Ad = 1-adamantyl), (C5Me5)2U(C5H5), and (C5Me5)2U(C5Me4H) are compared with (C5Me5)2U[N(SiMe3)2], (C5Me5)2U[CH(SiMe3)2], and (C5Me5)U[N(SiMe3)2]2. An improved synthesis of (C5Me5)2U(μ-Ph)2BPh2 was developed, which was used to synthesize (C5Me5)2U(C5Me4H). Since the X-ray crystal structure of (C5Me5)2U(OC6H2tBu2-2,6-Me-4) contained two very different molecules in the asymmetric unit with 115.7(5)° and 166.0(5)° U-O-Cipso angles, the (C5Me4H)2U(OC6H2tBu2-2,6-Me-4) and (C5Me5)2Ce(OC6H2tBu2-2,6-Me-4) analogues were synthesized and characterized by X-ray diffraction for comparison. Electrochemical studies in THF with a 100 mM [Bu4N][BPh4] supporting electrolyte showed U(IV)/U(III) and U(III)/U(II) redox couples for all the heteroleptic complexes except (C5Me5)2U(C5H5). Chemical reduction of all heteroleptic compounds formed dark blue solutions characteristic of U(II) when reacted with KC8 at -78 °C, but none formed isolable U(II) complexes. The targeted U(II) complexes, [(C5Me5)2U(OC6H2tBu2-2,6-Me-4)]1-, {(C5Me5)2U[CH(SiMe3)2]}1-, [(C5Me5)2U(C5H5)]1-, and [(C5Me5)2U(C5Me4H)]1-, were analyzed by density functional theory, and a 5f36d1 electron configuration was found to be the ground state in each case.
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