4 research outputs found
Electrochemical studies of tris(cyclopentadienyl)thorium and uranium complexes in the +2, +3, and +4 oxidation states.
CH Bond Activation via U(II) in the Reduction of Heteroleptic Bis(trimethylsilyl)amide U(III) Complexes
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Electrochemical studies of tris(cyclopentadienyl)thorium and uranium complexes in the +2, +3, and +4 oxidation states.
Electrochemical measurements on tris(cyclopentadienyl)thorium and uranium compounds in the +2, +3, and +4 oxidation states are reported with C5H3(SiMe3)2, C5H4SiMe3, and C5Me4H ligands. The reduction potentials for both U and Th complexes trend with the electron donating abilities of the cyclopentadienyl ligand. Thorium complexes have more negative An(iii)/An(ii) reduction potentials than the uranium analogs. Electrochemical measurements of isolated Th(ii) complexes indicated that the Th(iii)/Th(ii) couple was surprisingly similar to the Th(iv)/Th(iii) couple in Cp''-ligated complexes. This suggested that Th(ii) complexes could be prepared from Th(iv) precursors and this was demonstrated synthetically by isolation of directly from UV-visible spectroelectrochemical measurements and reactions of with elemental barium indicated that the thorium system undergoes sequential one electron transformations