{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/17899"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/17899","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Isotopic labelling applied to the infrared spectra of metal complexes","abstract":"The infrared spectra of pyridine adducts of first transition series metal(II) acetylacetonates are discussed in relation to the band shifts induced by ¹⁵N-labelling and deuteration of the pyridine ring and by metal ion substitution. ¹⁵N-Labelling aids in establishing the pyridine ring vibrations, while deuteration and metal substitution are more useful in assigning the νM-L frequencies. Results of the isotopic labelling study lead to a revision of previously-reported νM-O and vC---O frequencies. This technique also facilitates assignment of the νM-N vibrations, observed in the region below 200 cm⁻¹. The occurrence of these bands in this spectral region was expected because of the known relative weakness of the M-N bond strength in pyridine adducts. The effects on the spectra resulting from introduction of a variety of substituents into the pyridine ring are discussed on the basis of the electronic effects of the substituents. After allowing for mass effects, electron-withdrawing substituents are found to decrease νNi-N frequencies while electron-releasing substituents exert negligible effect on the νNi-N bands. An opposite trend is, however, observed for the νNi-O bands and is explained. An investigation of a series of aniline and p-toluidine complexes of first transition metal(II) isothiocyanates is reported.","abstract_html":"The infrared spectra of pyridine adducts of first transition series metal(II) acetylacetonates are discussed in relation to the band shifts induced by ¹⁵N-labelling and deuteration of the pyridine ring and by metal ion substitution. ¹⁵N-Labelling aids in establishing the pyridine ring vibrations, while deuteration and metal substitution are more useful in assigning the νM-L frequencies. Results of the isotopic labelling study lead to a revision of previously-reported νM-O and vC---O frequencies. This technique also facilitates assignment of the νM-N vibrations, observed in the region below 200 cm⁻¹. The occurrence of these bands in this spectral region was expected because of the known relative weakness of the M-N bond strength in pyridine adducts. The effects on the spectra resulting from introduction of a variety of substituents into the pyridine ring are discussed on the basis of the electronic effects of the substituents. After allowing for mass effects, electron-withdrawing substituents are found to decrease νNi-N frequencies while electron-releasing substituents exert negligible effect on the νNi-N bands. An opposite trend is, however, observed for the νNi-O bands and is explained. An investigation of a series of aniline and p-toluidine complexes of first transition metal(II) isothiocyanates is reported.","abstract_has_math":false,"creators":["Engelter, Carola"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Thornton, David A"],"committee_chairs":[],"committee_members":[],"year":1977,"date_issued":"1977","date_published":"1977","updated_at":"2026-07-22T22:23:44Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/17899","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Thornton, David A"]},{"key":"dc:creator","label":"Author","values":["Engelter, Carola"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-03-17T07:18:36Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-03-17T07:18:36Z"]},{"key":"dc:date.issued","label":"Date","values":["1977"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cape Town"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11427/17899"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The infrared spectra of pyridine adducts of first transition series metal(II) acetylacetonates are discussed in relation to the band shifts induced by ¹⁵N-labelling and deuteration of the pyridine ring and by metal ion substitution. ¹⁵N-Labelling aids in establishing the pyridine ring vibrations, while deuteration and metal substitution are more useful in assigning the νM-L frequencies. Results of the isotopic labelling study lead to a revision of previously-reported νM-O and vC---O frequencies. This technique also facilitates assignment of the νM-N vibrations, observed in the region below 200 cm⁻¹. The occurrence of these bands in this spectral region was expected because of the known relative weakness of the M-N bond strength in pyridine adducts. The effects on the spectra resulting from introduction of a variety of substituents into the pyridine ring are discussed on the basis of the electronic effects of the substituents. After allowing for mass effects, electron-withdrawing substituents are found to decrease νNi-N frequencies while electron-releasing substituents exert negligible effect on the νNi-N bands. An opposite trend is, however, observed for the νNi-O bands and is explained. An investigation of a series of aniline and p-toluidine complexes of first transition metal(II) isothiocyanates is reported."]},{"key":"dc:title","label":"Title","values":["Isotopic labelling applied to the infrared spectra of metal complexes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Thornton, David A"],"dc:creator":["Engelter, Carola"],"dc:date.accessioned":["2016-03-17T07:18:36Z"],"dc:date.available":["2016-03-17T07:18:36Z"],"dc:date.issued":["1977"],"dc:description.abstract":["The infrared spectra of pyridine adducts of first transition series metal(II) acetylacetonates are discussed in relation to the band shifts induced by ¹⁵N-labelling and deuteration of the pyridine ring and by metal ion substitution. ¹⁵N-Labelling aids in establishing the pyridine ring vibrations, while deuteration and metal substitution are more useful in assigning the νM-L frequencies. Results of the isotopic labelling study lead to a revision of previously-reported νM-O and vC---O frequencies. This technique also facilitates assignment of the νM-N vibrations, observed in the region below 200 cm⁻¹. The occurrence of these bands in this spectral region was expected because of the known relative weakness of the M-N bond strength in pyridine adducts. The effects on the spectra resulting from introduction of a variety of substituents into the pyridine ring are discussed on the basis of the electronic effects of the substituents. After allowing for mass effects, electron-withdrawing substituents are found to decrease νNi-N frequencies while electron-releasing substituents exert negligible effect on the νNi-N bands. An opposite trend is, however, observed for the νNi-O bands and is explained. An investigation of a series of aniline and p-toluidine complexes of first transition metal(II) isothiocyanates is reported."],"dc:identifier.uri":["http://hdl.handle.net/11427/17899"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Isotopic labelling applied to the infrared spectra of metal complexes"],"dc:type":["Doctoral Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-22T22:23:44Z"}