Synthesis of chromium complexes with bipyridine radican anions

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 reac...

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Main Author: Moisey, Luke
Language:English
Published: University of British Columbia 2015
Online Access:http://hdl.handle.net/2429/53993
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spelling ndltd-UBC-oai-circle.library.ubc.ca-2429-539932018-01-05T17:28:17Z 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. Irving K. Barber School of Arts and Sciences (Okanagan) Chemistry, Department of (Okanagan) Graduate 2015-07-02T17:16:20Z 2015-07-02T17:16:20Z 2015 2015-09 Text Thesis/Dissertation http://hdl.handle.net/2429/53993 eng Attribution-NonCommercial-NoDerivs 2.5 Canada http://creativecommons.org/licenses/by-nc-nd/2.5/ca/ University of British Columbia
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language English
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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. === Irving K. Barber School of Arts and Sciences (Okanagan) === Chemistry, Department of (Okanagan) === Graduate
author Moisey, Luke
spellingShingle Moisey, Luke
Synthesis of chromium complexes with bipyridine radican anions
author_facet Moisey, Luke
author_sort Moisey, Luke
title Synthesis of chromium complexes with bipyridine radican anions
title_short Synthesis of chromium complexes with bipyridine radican anions
title_full Synthesis of chromium complexes with bipyridine radican anions
title_fullStr Synthesis of chromium complexes with bipyridine radican anions
title_full_unstemmed Synthesis of chromium complexes with bipyridine radican anions
title_sort synthesis of chromium complexes with bipyridine radican anions
publisher University of British Columbia
publishDate 2015
url http://hdl.handle.net/2429/53993
work_keys_str_mv AT moiseyluke synthesisofchromiumcomplexeswithbipyridineradicananions
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