{"id":{"repo_id":"cent-lancashire","oai_identifier":"oai:clok.uclan.ac.uk:20983"},"canonical_url":"https://search.dev.ndltd.org/etd/cent-lancashire/oai:clok.uclan.ac.uk:20983","repository":{"repo_id":"cent-lancashire","name":"University of Central Lancashire","base_url":"https://clok.uclan.ac.uk/cgi/oai2"},"display":{"title":"The synthesis, characterisation and photochemistry of novel organometallic complexes","abstract":"Complexation of an organic ligand by a transition metal can radically alter the ligand photochemistry. In order to investigate these effects, we synthesised a series of organometallic complexes with several different modes of ligand-metal bonding. The synthesis of various cyclopentadienyl, arene, diene and enone complexes was attempted. Novel ferrocenyl fulgides, including several methoxy-substituted analogues were synthesised, and have been shown to display E/Z-photoisomerism. In contrast with the report by McVey et al,81 we showed that methoxyferrocene would not Friedel-Crafts acetylate in the 2- or 3-positions using aluminium chloride as the Lewis acid catalyst. Substitution only occurs at the 1'-position, which is thought to be due to deactivation of the methoxy-substituted ring by coordination of the aluminium chloride/acetyl chloride complex by the methoxy group. However, we successfully synthesised the 2- and 3-methoxyacetylferrocenes by replacing aluminium chloride by the more sterically demanding Lewis acid, diethylaluminium chloride. All attempts at using organic fulgides as diene or enone ligands with a series of metals has shown them to be totally unsuitable for this purpose. We succesfully synthesised a wide range of fulgide arene chromium tricarbonyl complexes. Their photochemistry was found to consist of simple E/Z-isomerisation followed by decomposition. However, their thermochemistry proved to be very interesting It was shown that a thermal electrocyclic ring closure reaction could be induced at considerably lower temperatures (i.e: -135°C ) than normal (i.e: -200°C) when a chromium tricarbonyl moiety is attached to the fulgide arene group. A crystal structure of the ring closed product from one of these fulgide chromium complexes shows that the Woodward-Hoffmann rules may have been broken by this metal-mediated ring closure. Efforts were being made to prove that this ring-closure reaction proceeded via a thermally forbidden conrotatory mechanism. Preliminary studies on the use of these chromium tricarbonyl fulgide complexes in the synthesis of hitherto inaccessible fulgides were carried out.","abstract_html":"Complexation of an organic ligand by a transition metal can radically alter the ligand photochemistry. In order to investigate these effects, we synthesised a series of organometallic complexes with several different modes of ligand-metal bonding. The synthesis of various cyclopentadienyl, arene, diene and enone complexes was attempted. Novel ferrocenyl fulgides, including several methoxy-substituted analogues were synthesised, and have been shown to display E/Z-photoisomerism. In contrast with the report by McVey et al,81 we showed that methoxyferrocene would not Friedel-Crafts acetylate in the 2- or 3-positions using aluminium chloride as the Lewis acid catalyst. Substitution only occurs at the 1'-position, which is thought to be due to deactivation of the methoxy-substituted ring by coordination of the aluminium chloride/acetyl chloride complex by the methoxy group. However, we successfully synthesised the 2- and 3-methoxyacetylferrocenes by replacing aluminium chloride by the more sterically demanding Lewis acid, diethylaluminium chloride. All attempts at using organic fulgides as diene or enone ligands with a series of metals has shown them to be totally unsuitable for this purpose. We succesfully synthesised a wide range of fulgide arene chromium tricarbonyl complexes. Their photochemistry was found to consist of simple E/Z-isomerisation followed by decomposition. However, their thermochemistry proved to be very interesting It was shown that a thermal electrocyclic ring closure reaction could be induced at considerably lower temperatures (i.e: -135°C ) than normal (i.e: -200°C) when a chromium tricarbonyl moiety is attached to the fulgide arene group. A crystal structure of the ring closed product from one of these fulgide chromium complexes shows that the Woodward-Hoffmann rules may have been broken by this metal-mediated ring closure. Efforts were being made to prove that this ring-closure reaction proceeded via a thermally forbidden conrotatory mechanism. Preliminary studies on the use of these chromium tricarbonyl fulgide complexes in the synthesis of hitherto inaccessible fulgides were carried out.","abstract_has_math":false,"creators":["Saberi, Stephen Philip"],"institution":"Lancashire Polytechnic","degree_name":"phd","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1990,"date_issued":"1990-10","date_published":"1990-10","updated_at":"2026-07-24T01:36:20Z","subjects":["F100 - Chemistry"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Saberi, Stephen Philip"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1990-10-01"]},{"key":"dc:date.issued","label":"Date","values":["1990-10"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["Lancashire Polytechnic"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://knowledge.lancashire.ac.uk/id/eprint/20983/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["phd"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["F100 - Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://knowledge.lancashire.ac.uk/id/eprint/20983/1/20983%20Stephen%20Philip%20Saberi%20Oct90%20the%20synthesis%2C%20characterisation%20and%20photochemistry%20of%20novel%20organometallic%20complexes%20Doctor%20of%20Philosophy%20unpublished%20Oct90%20University%20of%20Central%20Lancashire%20chemistry%20240.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Complexation of an organic ligand by a transition metal can radically alter the ligand photochemistry. In order to investigate these effects, we synthesised a series of organometallic complexes with several different modes of ligand-metal bonding. The synthesis of various cyclopentadienyl, arene, diene and enone complexes was attempted. Novel ferrocenyl fulgides, including several methoxy-substituted analogues were synthesised, and have been shown to display E/Z-photoisomerism. In contrast with the report by McVey et al,81 we showed that methoxyferrocene would not Friedel-Crafts acetylate in the 2- or 3-positions using aluminium chloride as the Lewis acid catalyst. Substitution only occurs at the 1'-position, which is thought to be due to deactivation of the methoxy-substituted ring by coordination of the aluminium chloride/acetyl chloride complex by the methoxy group. However, we successfully synthesised the 2- and 3-methoxyacetylferrocenes by replacing aluminium chloride by the more sterically demanding Lewis acid, diethylaluminium chloride. All attempts at using organic fulgides as diene or enone ligands with a series of metals has shown them to be totally unsuitable for this purpose. We succesfully synthesised a wide range of fulgide arene chromium tricarbonyl complexes. Their photochemistry was found to consist of simple E/Z-isomerisation followed by decomposition. However, their thermochemistry proved to be very interesting It was shown that a thermal electrocyclic ring closure reaction could be induced at considerably lower temperatures (i.e: -135°C ) than normal (i.e: -200°C) when a chromium tricarbonyl moiety is attached to the fulgide arene group. A crystal structure of the ring closed product from one of these fulgide chromium complexes shows that the Woodward-Hoffmann rules may have been broken by this metal-mediated ring closure. Efforts were being made to prove that this ring-closure reaction proceeded via a thermally forbidden conrotatory mechanism. Preliminary studies on the use of these chromium tricarbonyl fulgide complexes in the synthesis of hitherto inaccessible fulgides were carried out."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The synthesis, characterisation and photochemistry of novel organometallic complexes"]}]}],"canonical_facts":{"dc:creator":["Saberi, Stephen Philip"],"dc:date":["1990-10-01"],"dc:date.issued":["1990-10"],"dc:description.abstract":["Complexation of an organic ligand by a transition metal can radically alter the ligand photochemistry. In order to investigate these effects, we synthesised a series of organometallic complexes with several different modes of ligand-metal bonding. The synthesis of various cyclopentadienyl, arene, diene and enone complexes was attempted. Novel ferrocenyl fulgides, including several methoxy-substituted analogues were synthesised, and have been shown to display E/Z-photoisomerism. In contrast with the report by McVey et al,81 we showed that methoxyferrocene would not Friedel-Crafts acetylate in the 2- or 3-positions using aluminium chloride as the Lewis acid catalyst. Substitution only occurs at the 1'-position, which is thought to be due to deactivation of the methoxy-substituted ring by coordination of the aluminium chloride/acetyl chloride complex by the methoxy group. However, we successfully synthesised the 2- and 3-methoxyacetylferrocenes by replacing aluminium chloride by the more sterically demanding Lewis acid, diethylaluminium chloride. All attempts at using organic fulgides as diene or enone ligands with a series of metals has shown them to be totally unsuitable for this purpose. We succesfully synthesised a wide range of fulgide arene chromium tricarbonyl complexes. Their photochemistry was found to consist of simple E/Z-isomerisation followed by decomposition. However, their thermochemistry proved to be very interesting It was shown that a thermal electrocyclic ring closure reaction could be induced at considerably lower temperatures (i.e: -135°C ) than normal (i.e: -200°C) when a chromium tricarbonyl moiety is attached to the fulgide arene group. A crystal structure of the ring closed product from one of these fulgide chromium complexes shows that the Woodward-Hoffmann rules may have been broken by this metal-mediated ring closure. Efforts were being made to prove that this ring-closure reaction proceeded via a thermally forbidden conrotatory mechanism. Preliminary studies on the use of these chromium tricarbonyl fulgide complexes in the synthesis of hitherto inaccessible fulgides were carried out."],"dc:format":["application/pdf"],"dc:identifier.uri":["https://knowledge.lancashire.ac.uk/id/eprint/20983/1/20983%20Stephen%20Philip%20Saberi%20Oct90%20the%20synthesis%2C%20characterisation%20and%20photochemistry%20of%20novel%20organometallic%20complexes%20Doctor%20of%20Philosophy%20unpublished%20Oct90%20University%20of%20Central%20Lancashire%20chemistry%20240.pdf"],"dc:language":["en"],"dc:publisher.department":["School of Chemistry"],"dc:publisher.institution":["Lancashire Polytechnic"],"dc:relation.isreferencedby":["https://knowledge.lancashire.ac.uk/id/eprint/20983/"],"dc:subject":["F100 - Chemistry"],"dc:title":["The synthesis, characterisation and photochemistry of novel organometallic complexes"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T01:36:20Z"}