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UBC Theses and Dissertations
Synthesis of chromium complexes with bipyridine radican anions Moisey, Luke
Abstract
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.
Item Metadata
Title |
Synthesis of chromium complexes with bipyridine radican anions
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
2015
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Description |
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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Genre | |
Type | |
Language |
eng
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Date Available |
2015-07-02
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Provider |
Vancouver : University of British Columbia Library
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Rights |
Attribution-NonCommercial-NoDerivs 2.5 Canada
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DOI |
10.14288/1.0166343
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
2015-09
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Campus | |
Scholarly Level |
Graduate
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Rights URI | |
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DSpace
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Attribution-NonCommercial-NoDerivs 2.5 Canada