{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/9971"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/9971","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"A structural investigation of the mercury-sulphur interaction","abstract":"The crystal and molecular structures of phenyl, 2-mercaptopyrimidine mercury(II) and phenyl,mercaptobenzene mercury(II) have been determined by the methods of X-ray crystallography. The interaction between mercury and sulphur is investigated. This interaction is of interest both biochemically and toxicologically. More specifically, secondary Hg---S interactions are found to mimic that observed in NMR exchange processes, where they undergo a transition state as a four-membered bridging intermediate. Structural correlations between compounds containing at least one mercury - sulphur covalent bond are examined. The coordination geometry about the mercury atom is generally found to be distorted tetrahedra or octahedra, with a very strong tendency to retain the linear character of the R - Hg - S angle. The electronegativity of sulphur is found to be the most influential parameter in determining the coordination geonetry of the mercury atom. The transition from four- to six-coordinated structures is examined but did not reveal unambiguously whether this occurs by an SN3 or (SN2)2 disubstitution process. The four-membered bridging structure formed by secondary Hg---S interactions is investigated to determine whether minimum energy pathways are evident. However, there is no evidence for pathways representing exchange as observed in solution.","abstract_html":"The crystal and molecular structures of phenyl, 2-mercaptopyrimidine mercury(II) and phenyl,mercaptobenzene mercury(II) have been determined by the methods of X-ray crystallography. The interaction between mercury and sulphur is investigated. This interaction is of interest both biochemically and toxicologically. More specifically, secondary Hg---S interactions are found to mimic that observed in NMR exchange processes, where they undergo a transition state as a four-membered bridging intermediate. Structural correlations between compounds containing at least one mercury - sulphur covalent bond are examined. The coordination geometry about the mercury atom is generally found to be distorted tetrahedra or octahedra, with a very strong tendency to retain the linear character of the R - Hg - S angle. The electronegativity of sulphur is found to be the most influential parameter in determining the coordination geonetry of the mercury atom. The transition from four- to six-coordinated structures is examined but did not reveal unambiguously whether this occurs by an SN3 or (SN2)2 disubstitution process. The four-membered bridging structure formed by secondary Hg---S interactions is investigated to determine whether minimum energy pathways are evident. However, there is no evidence for pathways representing exchange as observed in solution.","abstract_has_math":false,"creators":["Dijkstra, Ellemieke"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Nassimbeni, Luigi R"],"committee_chairs":[],"committee_members":[],"year":1982,"date_issued":"1982","date_published":"1982","updated_at":"2026-07-22T22:23:27Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/9971","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Nassimbeni, Luigi R"]},{"key":"dc:creator","label":"Author","values":["Dijkstra, Ellemieke"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-12-11T21:00:02Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-12-11T21:00:02Z"]},{"key":"dc:date.issued","label":"Date","values":["1982"]},{"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":["Master Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Masters"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["MSc"]}]},{"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/11427/9971"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Bibliography: p. 130-136."]},{"key":"dc:description.abstract","label":"Abstract","values":["The crystal and molecular structures of phenyl, 2-mercaptopyrimidine mercury(II) and phenyl,mercaptobenzene mercury(II) have been determined by the methods of X-ray crystallography. The interaction between mercury and sulphur is investigated. This interaction is of interest both biochemically and toxicologically. More specifically, secondary Hg---S interactions are found to mimic that observed in NMR exchange processes, where they undergo a transition state as a four-membered bridging intermediate. Structural correlations between compounds containing at least one mercury - sulphur covalent bond are examined. The coordination geometry about the mercury atom is generally found to be distorted tetrahedra or octahedra, with a very strong tendency to retain the linear character of the R - Hg - S angle. The electronegativity of sulphur is found to be the most influential parameter in determining the coordination geonetry of the mercury atom. The transition from four- to six-coordinated structures is examined but did not reveal unambiguously whether this occurs by an SN3 or (SN2)2 disubstitution process. The four-membered bridging structure formed by secondary Hg---S interactions is investigated to determine whether minimum energy pathways are evident. However, there is no evidence for pathways representing exchange as observed in solution."]},{"key":"dc:title","label":"Title","values":["A structural investigation of the mercury-sulphur interaction"]}]}],"canonical_facts":{"dc:contributor.advisor":["Nassimbeni, Luigi R"],"dc:creator":["Dijkstra, Ellemieke"],"dc:date.accessioned":["2014-12-11T21:00:02Z"],"dc:date.available":["2014-12-11T21:00:02Z"],"dc:date.issued":["1982"],"dc:description":["Bibliography: p. 130-136."],"dc:description.abstract":["The crystal and molecular structures of phenyl, 2-mercaptopyrimidine mercury(II) and phenyl,mercaptobenzene mercury(II) have been determined by the methods of X-ray crystallography. The interaction between mercury and sulphur is investigated. This interaction is of interest both biochemically and toxicologically. More specifically, secondary Hg---S interactions are found to mimic that observed in NMR exchange processes, where they undergo a transition state as a four-membered bridging intermediate. Structural correlations between compounds containing at least one mercury - sulphur covalent bond are examined. The coordination geometry about the mercury atom is generally found to be distorted tetrahedra or octahedra, with a very strong tendency to retain the linear character of the R - Hg - S angle. The electronegativity of sulphur is found to be the most influential parameter in determining the coordination geonetry of the mercury atom. The transition from four- to six-coordinated structures is examined but did not reveal unambiguously whether this occurs by an SN3 or (SN2)2 disubstitution process. The four-membered bridging structure formed by secondary Hg---S interactions is investigated to determine whether minimum energy pathways are evident. However, there is no evidence for pathways representing exchange as observed in solution."],"dc:identifier.uri":["http://hdl.handle.net/11427/9971"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["A structural investigation of the mercury-sulphur interaction"],"dc:type":["Master Thesis"],"dc:type.qualificationlevel":["Masters"],"dc:type.qualificationname":["MSc"]},"updated_at":"2026-07-22T22:23:27Z"}