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Electrochemical behaviour of some organometallic compounds containing iron and molybdenum
The electrochemical behaviour of some mononuclear alkyl compounds of the types CpFe(CO)₂(CH₂)nCH₃ (n = 0 to 11, Cp = η-C₅H₅), CpMo(CO)₃(CH₂)nCH₃ (n = 3,4,17) have been investigated in aprotic solvents. The cyclic voltammograms obtained for all the iron alkyl compounds suggest similar behaviour after...
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| Format: | Thesis |
| Language: | English |
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Department of Chemistry
2016
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| _version_ | 1867613237915156480 |
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| access_status_str | Open Access |
| author | Daries, Keith Louis |
| author2 | Moss, John R |
| author_browse | Daries, Keith Louis Moss, John R |
| author_facet | Moss, John R Daries, Keith Louis |
| author_sort | Daries, Keith Louis |
| collection | Thesis |
| description | The electrochemical behaviour of some mononuclear alkyl compounds of the types CpFe(CO)₂(CH₂)nCH₃ (n = 0 to 11, Cp = η-C₅H₅), CpMo(CO)₃(CH₂)nCH₃ (n = 3,4,17) have been investigated in aprotic solvents. The cyclic voltammograms obtained for all the iron alkyl compounds suggest similar behaviour after the initial oxidation. The oxidation potentials showed no linear correlation with the corresponding lengths of the alkyl chain, but could, however, be interpreted with the available Tolman's χ-values. The subsequent CO insertion reaction to give an acyl species was found to be dependent on the nucleophilicity of the solvent. The relative rates of decarbonylation of the acyl species could be assessed through cyclic voltammetry. The electrochemical behaviour of heterobimetallic complexes of the type CpFe(CO)₂(CH₂)nMo(CO)₃Cp (n = 3 to 6) was found to be solvent dependent. The anodic waves obtained for these complexes in acetonitrile showed up as two closely spaced waves. Our results suggest that the two metals in CpFe(CO)₂(CH)nMo(CO)₃Cp behave independently, with the iron end of the molecule being oxidized first, followed by CO insertion/alkyl migration at this end. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/18619 |
| institution | University of Cape Town (South Africa) |
| language | eng |
| last_indexed | 2026-06-10T12:32:57.328Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository |
| publishDate | 2016 |
| publishDateRange | 2016 |
| publishDateSort | 2016 |
| publisher | Department of Chemistry |
| publisherStr | Department of Chemistry |
| record_format | dspace |
| source_str | UCTD — University of Cape Town Open Access Repository |
| spelling | oai:open.uct.ac.za:11427/18619 Electrochemical behaviour of some organometallic compounds containing iron and molybdenum Daries, Keith Louis Moss, John R Chemistry The electrochemical behaviour of some mononuclear alkyl compounds of the types CpFe(CO)₂(CH₂)nCH₃ (n = 0 to 11, Cp = η-C₅H₅), CpMo(CO)₃(CH₂)nCH₃ (n = 3,4,17) have been investigated in aprotic solvents. The cyclic voltammograms obtained for all the iron alkyl compounds suggest similar behaviour after the initial oxidation. The oxidation potentials showed no linear correlation with the corresponding lengths of the alkyl chain, but could, however, be interpreted with the available Tolman's χ-values. The subsequent CO insertion reaction to give an acyl species was found to be dependent on the nucleophilicity of the solvent. The relative rates of decarbonylation of the acyl species could be assessed through cyclic voltammetry. The electrochemical behaviour of heterobimetallic complexes of the type CpFe(CO)₂(CH₂)nMo(CO)₃Cp (n = 3 to 6) was found to be solvent dependent. The anodic waves obtained for these complexes in acetonitrile showed up as two closely spaced waves. Our results suggest that the two metals in CpFe(CO)₂(CH)nMo(CO)₃Cp behave independently, with the iron end of the molecule being oxidized first, followed by CO insertion/alkyl migration at this end. 2016-04-05T11:48:07Z 2016-04-05T11:48:07Z 1996 Master Thesis Masters MSc http://hdl.handle.net/11427/18619 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Chemistry Daries, Keith Louis Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| thesis_degree_str | Master's |
| title | Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| title_full | Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| title_fullStr | Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| title_full_unstemmed | Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| title_short | Electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| title_sort | electrochemical behaviour of some organometallic compounds containing iron and molybdenum |
| topic | Chemistry |
| url | http://hdl.handle.net/11427/18619 |
| work_keys_str_mv | AT darieskeithlouis electrochemicalbehaviourofsomeorganometalliccompoundscontainingironandmolybdenum |