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UBC Theses and Dissertations

Synthesis of chromium complexes with bipyridine radican anions Moisey, Luke


This thesis describes the synthesis of new, well-defined paramagnetic inorganic and organometallic molecules that contain the metal chromium. Throughout this thesis, 2,2’-bipyridines (Rbpy, R=H, CMe₃) are used as an ancillary redox active ligand and explored for potential radical character. The reaction of Cr[N(SiMe₃)₂]₂(THF)₂ with Ph-nacnacH yielded Cr(Ph-nacnac)[N(SiMe₃)₂]. The bound amide ligand can be removed through protonation with [tbpyH][BPh₄] and tbpy to afford the octahedral [Cr(Ph-nacnac)(tbpy)₃][BPh₄] complex with a single unpaired electron on the tbpy ligands. Reaction of Cr(bpy)[N(SiMe₃)₂]₂ with two equivalents of 8-hydroxyquinoline affords the octahedral complex, Cr(bpy)(8-hydroxyquinoline)₂, where the LX• radical is now centred on the single tbpy ligand. Protonation to remove the amides in Cr[N(SiMe₃)₂]₂(THF)₂ with 2-aminodiphenylamine yielded the tetrameric [Cr(μ-NHC₆H₄-2-μ-NC₆H₅)]₄ complex. CrCl₂(tBu-acac)(tbpy) reacted with AgO₂CPh to yield the trans carboxylate Cr(O₂CPh)₂(tbpy)(tBu-acac) with a neutral tbpy ligand. Subsequent reactions with the chromium dichloride with PhMgCl yielded a [CrPh₃(tbpy)][Mg(tBu-acac)(THF)₄] complex. The complex is an unusual square-pyramidal anionic complex with a tbpy based radical.

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