- Library Home /
- Search Collections /
- Open Collections /
- Browse Collections /
- UBC Undergraduate Research /
- Rapid Synthesis of Ligand-Based Radicals from Chromium(II)...
Open Collections
UBC Undergraduate Research
Rapid Synthesis of Ligand-Based Radicals from Chromium(II) Compounds Desnoyer, Addison
Abstract
The existence of metal complexes that contain ligand-based radicals has been known for years, yet has mainly been regarded as a spectroscopic oddity. More recently, the effects of these redox non-innocent ligands on the reactivities of first-row transition metals during catalytic processes has been examined. In an effort to study the reactivities of some of these complexes, a series of octahedral Cr(III) complexes with both redox innocent and non-innocent ligands was synthesized. The square planar Cr(II) compound Cr(DPM)2 was found to be an excellent single electron reductant for a variety of neutral diimines to give the corresponding octahedral Cr(DPM)2(LX•) complexes. In addition, the use of a variety of Cr(II) compounds as single electron reductant prior to protonolysis of the resulting Cr(bpy) complex with a variety of ligands of the form H(R,R’-acac) was found to give the corresponding Cr(R,R’-acac)2(bpy•) complex, allowing for greater tuning of the ancillary ligands. The radical complexes were found to be intensely coloured and air sensitive, and were primarily characterized by UV/vis spectrophotometry. In addition, the complex Cr(DPM)2(bpy•) was found to rapidly and quantitatively react with trityl bromide via an outer-sphere single electron transfer mechanism, generating the trityl radical and the cationic Cr(DPM)2(bpy) complex.
Item Metadata
| Title |
Rapid Synthesis of Ligand-Based Radicals from Chromium(II) Compounds
|
| Creator | |
| Date Issued |
2011-04
|
| Description |
The existence of metal complexes that contain ligand-based radicals has been known for years, yet has mainly been regarded as a spectroscopic oddity. More recently, the effects of these redox non-innocent ligands on the reactivities of first-row transition metals during catalytic processes has been examined. In an effort to study the reactivities of some of these complexes, a series of octahedral Cr(III) complexes with both redox innocent and non-innocent ligands was synthesized. The square planar Cr(II) compound Cr(DPM)2 was found to be an excellent single electron reductant for a variety of neutral diimines to give the corresponding octahedral Cr(DPM)2(LX•) complexes. In addition, the use of a variety of Cr(II) compounds as single electron reductant prior to protonolysis of the resulting Cr(bpy) complex with a variety of ligands of the form H(R,R’-acac) was found to give the corresponding Cr(R,R’-acac)2(bpy•) complex, allowing for greater tuning of the ancillary ligands. The radical complexes were found to be intensely coloured and air sensitive, and were primarily characterized by UV/vis spectrophotometry. In addition, the complex Cr(DPM)2(bpy•) was found to rapidly and quantitatively react with trityl bromide via an outer-sphere single electron transfer mechanism, generating the trityl radical and the cationic Cr(DPM)2(bpy) complex.
|
| Subject | |
| Genre | |
| Type | |
| Language |
eng
|
| Series | |
| Date Available |
2011-06-06
|
| Provider |
Vancouver : University of British Columbia Library
|
| Rights |
Attribution-NonCommercial-NoDerivatives 4.0 International
|
| DOI |
10.14288/1.0048182
|
| URI | |
| Affiliation | |
| Campus | |
| Peer Review Status |
Unreviewed
|
| Scholarly Level |
Undergraduate
|
| Rights URI | |
| Aggregated Source Repository |
DSpace
|
Item Media
Item Citations and Data
Rights
Attribution-NonCommercial-NoDerivatives 4.0 International