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The synthesis and reactivity of functionalised alkyl transition metal complexes
Includes bibliographical references.
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| Main Author: | |
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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Department of Chemistry
2016
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| _version_ | 1867613237398208513 |
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| access_status_str | Open Access |
| author | Friedrich, Holger Bernhard |
| author2 | Moss, John R |
| author_browse | Friedrich, Holger Bernhard Moss, John R |
| author_facet | Moss, John R Friedrich, Holger Bernhard |
| author_sort | Friedrich, Holger Bernhard |
| collection | Thesis |
| description | Includes bibliographical references. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/22277 |
| 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:11427/22277 The synthesis and reactivity of functionalised alkyl transition metal complexes Friedrich, Holger Bernhard Moss, John R Chemistry Inorganic Chemistry Includes bibliographical references. The complexes [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] (Cp = n⁵-C₅H₅; X=Cl, Br, I) have been prepared and their reactivity with a series of tertiary phosphines, amines, SMe₂ and AsPh₃ in THF, CH₃CN and MeOH has been investigated. Two types of cationic products, namely the ylide complexes [CpM(CO)nCH₂L]+ or the disubstituted complexes [CpML₂(CO)n-l]+ (M = Fe, n = 2; M = W, n = 3) were obtained, depending on the halide (X), the ligand (L), the metal (M) and the solvent used. The variables X, L, M and the solvent used were also all found to influence the rates of the reactions. Thus the relative reaction rates of the complexes [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with L were determined by 1 H NMR spectroscopy and found to increase with increasing pKa and decreasing cone angle of L. In general, the rate of reaction of [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] with L increases in the sequence Cl < Br < l and the reactions of [CpFe(CO)₂CH₂X] with L are significantly faster than the corresponding reactions of [CpW(CO)₃CH₂X]. The reactions of [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with dppe {dppe = bis(diphenylphosphino)ethane} yield the bridged dicationic ylide complexes [{Cp(CO)₂FeCH₂}₂{PPh₂(CH₂)₂PPh₂}] and [{Cp(CO)₃WCH₂}₂{PPh₂(CH₂)₂PPh₂}] respectively. 2016-10-24T03:50:38Z 2016-10-24T03:50:38Z 1990 Doctoral Thesis Doctoral PhD http://hdl.handle.net/11427/22277 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Chemistry Inorganic Chemistry Friedrich, Holger Bernhard The synthesis and reactivity of functionalised alkyl transition metal complexes |
| thesis_degree_str | Doctoral |
| title | The synthesis and reactivity of functionalised alkyl transition metal complexes |
| title_full | The synthesis and reactivity of functionalised alkyl transition metal complexes |
| title_fullStr | The synthesis and reactivity of functionalised alkyl transition metal complexes |
| title_full_unstemmed | The synthesis and reactivity of functionalised alkyl transition metal complexes |
| title_short | The synthesis and reactivity of functionalised alkyl transition metal complexes |
| title_sort | synthesis and reactivity of functionalised alkyl transition metal complexes |
| topic | Chemistry Inorganic Chemistry |
| url | http://hdl.handle.net/11427/22277 |
| work_keys_str_mv | AT friedrichholgerbernhard thesynthesisandreactivityoffunctionalisedalkyltransitionmetalcomplexes AT friedrichholgerbernhard synthesisandreactivityoffunctionalisedalkyltransitionmetalcomplexes |