{"id":{"repo_id":"waikato-masters","oai_identifier":"oai:researchcommons.waikato.ac.nz:10289/16237"},"canonical_url":"https://search.dev.ndltd.org/etd/waikato-masters/oai:researchcommons.waikato.ac.nz:10289/16237","repository":{"repo_id":"waikato-masters","name":"University Waikato","base_url":"https://researchcommons.waikato.ac.nz/server/oai/request"},"display":{"title":"The reactions of group IVB hydrides with carbonyl complexes of cobalt and manganese","abstract":"The use of the hydrides as reagents for building group IVB - transition metal complexes has been investigated. The reactions of the simple hydrides; Me₃GeH, Me₂GeH₂, MeGeH₃, GeH₄, Me₂SiH₂, Me₂SnH₂, MeSnH₃, and SnH₄, with Co₂(CO)₈ have been examined, and the effect determined of, reactant ratios and amount of CO present, on the products obtained. Limited evidence was obtained for the synthesis of the new compounds; MeGe[Co(CO)₄]₃, HGe[Co(CO)₄]₃, Me₂SiHCo(CO)₄ and (OC)₄CoMe₂SiOCCo₃(CO)₉. Me₂GeH₂ replaces a bridging CO group: Me₂GeH₂ + Co₂(CO)₈ → Me₂GeCo₂(CO)₇ + H₂ + CO Me₂GeH₂ + Me₂GeCo₂(CO) ₇ → (Me₂Ge)₂Co₂(CO)₆ + H₂ + CO In the reactions of the polygermanes; Me₃GeGeH₃, Me₃SiGeH₃, Ge₂H₆, Ge₃H₈ and (GeH₃)₂SiMe₂ with Co₂(CO)₈, the M'-Ge, (M' = Si or Ge) bonds were quantitatively cleaved, and the new compound Ge₂Co₆(CO)₂₀, was isolated. This compound is assigned the structure: on spectroscopic evidence. Me₂GeH₂ also replaces a bridging CO group in the germanium - cobalt carbonyl species, to produce the new compounds; Me₂Ge₂Co₄(CO)₁₃ and (Me₂Ge)₂Ge₂Co₆(CO)₁₈. An X-ray crystallographic study on Me₂Ge₂Co₄(CO)₁₃ although showing the: skeleton, failed to refine properly. The reactions of Me₂SiH₂ and Me₂SnH₂ with germanium - cobalt carbonyl species failed to give a similar result. MeGeH₃ and GeCo₄(Co)₁₄ produced initially the analogous Me(H)Ge₂Co₄(CO)₁₃. However when left for 6 months, an unexpected rearrangement yielded (MeGe)₂Co₄(CO)₁₁. X-ray crystallography showed an irregular square bipyramidal structure, containing 5-coordinated square pyramidal germanium. This is this first example of such a group IVB - transition metal cluster. The decarbonylation of Ge₂Co₆(CO)₂₀ yielded the new compound [(OC)₄CoGe]₂Co₄(CO)₁₁ : which was found by X-ray crystallography to have a similar square bipyramidal structure. The new tin hydrides; MeSnH₂Mn(CO)₅ and Me₂SnHMn(CO)₅, have been prepared by the established route : Me₍₃₋ₓ₎SnHₓCl + NaMn(CO)₅ → Me₍₃₋ₓ₎SnHₓMn(CO)₅ + NaCl (x = 1,2) and characterised spectroscopically.","abstract_html":"The use of the hydrides as reagents for building group IVB - transition metal complexes has been investigated. The reactions of the simple hydrides; Me₃GeH, Me₂GeH₂, MeGeH₃, GeH₄, Me₂SiH₂, Me₂SnH₂, MeSnH₃, and SnH₄, with Co₂(CO)₈ have been examined, and the effect determined of, reactant ratios and amount of CO present, on the products obtained. Limited evidence was obtained for the synthesis of the new compounds; MeGe[Co(CO)₄]₃, HGe[Co(CO)₄]₃, Me₂SiHCo(CO)₄ and (OC)₄CoMe₂SiOCCo₃(CO)₉. Me₂GeH₂ replaces a bridging CO group: Me₂GeH₂ + Co₂(CO)₈ → Me₂GeCo₂(CO)₇ + H₂ + CO Me₂GeH₂ + Me₂GeCo₂(CO) ₇ → (Me₂Ge)₂Co₂(CO)₆ + H₂ + CO In the reactions of the polygermanes; Me₃GeGeH₃, Me₃SiGeH₃, Ge₂H₆, Ge₃H₈ and (GeH₃)₂SiMe₂ with Co₂(CO)₈, the M'-Ge, (M' = Si or Ge) bonds were quantitatively cleaved, and the new compound Ge₂Co₆(CO)₂₀, was isolated. This compound is assigned the structure: on spectroscopic evidence. Me₂GeH₂ also replaces a bridging CO group in the germanium - cobalt carbonyl species, to produce the new compounds; Me₂Ge₂Co₄(CO)₁₃ and (Me₂Ge)₂Ge₂Co₆(CO)₁₈. An X-ray crystallographic study on Me₂Ge₂Co₄(CO)₁₃ although showing the: skeleton, failed to refine properly. The reactions of Me₂SiH₂ and Me₂SnH₂ with germanium - cobalt carbonyl species failed to give a similar result. MeGeH₃ and GeCo₄(Co)₁₄ produced initially the analogous Me(H)Ge₂Co₄(CO)₁₃. However when left for 6 months, an unexpected rearrangement yielded (MeGe)₂Co₄(CO)₁₁. X-ray crystallography showed an irregular square bipyramidal structure, containing 5-coordinated square pyramidal germanium. This is this first example of such a group IVB - transition metal cluster. The decarbonylation of Ge₂Co₆(CO)₂₀ yielded the new compound [(OC)₄CoGe]₂Co₄(CO)₁₁ : which was found by X-ray crystallography to have a similar square bipyramidal structure. The new tin hydrides; MeSnH₂Mn(CO)₅ and Me₂SnHMn(CO)₅, have been prepared by the established route : Me₍₃₋ₓ₎SnHₓCl + NaMn(CO)₅ → Me₍₃₋ₓ₎SnHₓMn(CO)₅ + NaCl (x = 1,2) and characterised spectroscopically.","abstract_has_math":false,"creators":["Foster, Stephen Paul"],"institution":"The University of Waikato","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Mackay, Kenneth M.","Nicholson, Brian K."],"committee_chairs":[],"committee_members":[],"year":1982,"date_issued":"1982","date_published":"1982","updated_at":"2026-07-24T05:57:55Z","subjects":[],"languages":[],"rights":["All items in Research Commons are provided for private study and research purposes and are protected by copyright with all rights reserved unless otherwise indicated."],"rights_urls":["https://researchcommons.waikato.ac.nz/bitstreams/b109eeef-d4a8-4021-921f-966a2f426818/download"],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Mackay, Kenneth M.","Nicholson, Brian K."]},{"key":"dc:creator","label":"Author","values":["Foster, Stephen Paul"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["1982"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["The University of Waikato"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://hdl.handle.net/10289/16237"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["https://researchcommons.waikato.ac.nz/bitstreams/b109eeef-d4a8-4021-921f-966a2f426818/download","All items in Research Commons are provided for private study and research purposes and are protected by copyright with all rights reserved unless otherwise indicated."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://researchcommons.waikato.ac.nz/bitstreams/76eaaa91-89e2-4be9-a23e-ef17b85b83e7/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The use of the hydrides as reagents for building group IVB - transition metal complexes has been investigated. The reactions of the simple hydrides; Me₃GeH, Me₂GeH₂, MeGeH₃, GeH₄, Me₂SiH₂, Me₂SnH₂, MeSnH₃, and SnH₄, with Co₂(CO)₈ have been examined, and the effect determined of, reactant ratios and amount of CO present, on the products obtained. Limited evidence was obtained for the synthesis of the new compounds; MeGe[Co(CO)₄]₃, HGe[Co(CO)₄]₃, Me₂SiHCo(CO)₄ and (OC)₄CoMe₂SiOCCo₃(CO)₉. Me₂GeH₂ replaces a bridging CO group: Me₂GeH₂ + Co₂(CO)₈ → Me₂GeCo₂(CO)₇ + H₂ + CO Me₂GeH₂ + Me₂GeCo₂(CO) ₇ → (Me₂Ge)₂Co₂(CO)₆ + H₂ + CO In the reactions of the polygermanes; Me₃GeGeH₃, Me₃SiGeH₃, Ge₂H₆, Ge₃H₈ and (GeH₃)₂SiMe₂ with Co₂(CO)₈, the M'-Ge, (M' = Si or Ge) bonds were quantitatively cleaved, and the new compound Ge₂Co₆(CO)₂₀, was isolated. This compound is assigned the structure: on spectroscopic evidence. Me₂GeH₂ also replaces a bridging CO group in the germanium - cobalt carbonyl species, to produce the new compounds; Me₂Ge₂Co₄(CO)₁₃ and (Me₂Ge)₂Ge₂Co₆(CO)₁₈. An X-ray crystallographic study on Me₂Ge₂Co₄(CO)₁₃ although showing the: skeleton, failed to refine properly. The reactions of Me₂SiH₂ and Me₂SnH₂ with germanium - cobalt carbonyl species failed to give a similar result. MeGeH₃ and GeCo₄(Co)₁₄ produced initially the analogous Me(H)Ge₂Co₄(CO)₁₃. However when left for 6 months, an unexpected rearrangement yielded (MeGe)₂Co₄(CO)₁₁. X-ray crystallography showed an irregular square bipyramidal structure, containing 5-coordinated square pyramidal germanium. This is this first example of such a group IVB - transition metal cluster. The decarbonylation of Ge₂Co₆(CO)₂₀ yielded the new compound [(OC)₄CoGe]₂Co₄(CO)₁₁ : which was found by X-ray crystallography to have a similar square bipyramidal structure. The new tin hydrides; MeSnH₂Mn(CO)₅ and Me₂SnHMn(CO)₅, have been prepared by the established route : Me₍₃₋ₓ₎SnHₓCl + NaMn(CO)₅ → Me₍₃₋ₓ₎SnHₓMn(CO)₅ + NaCl (x = 1,2) and characterised spectroscopically."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["5bdc1977f020a4b0930b5c005c474b43","e14202ab27e47ddb00d33097327ba050","27fc56b47ea9ef15266dad350b1d134c"]},{"key":"dc:title","label":"Title","values":["The reactions of group IVB hydrides with carbonyl complexes of cobalt and manganese"]}]}],"canonical_facts":{"dc:contributor.advisor":["Mackay, Kenneth M.","Nicholson, Brian K."],"dc:creator":["Foster, Stephen Paul"],"dc:date.issued":["1982"],"dc:description.abstract":["The use of the hydrides as reagents for building group IVB - transition metal complexes has been investigated. The reactions of the simple hydrides; Me₃GeH, Me₂GeH₂, MeGeH₃, GeH₄, Me₂SiH₂, Me₂SnH₂, MeSnH₃, and SnH₄, with Co₂(CO)₈ have been examined, and the effect determined of, reactant ratios and amount of CO present, on the products obtained. Limited evidence was obtained for the synthesis of the new compounds; MeGe[Co(CO)₄]₃, HGe[Co(CO)₄]₃, Me₂SiHCo(CO)₄ and (OC)₄CoMe₂SiOCCo₃(CO)₉. Me₂GeH₂ replaces a bridging CO group: Me₂GeH₂ + Co₂(CO)₈ → Me₂GeCo₂(CO)₇ + H₂ + CO Me₂GeH₂ + Me₂GeCo₂(CO) ₇ → (Me₂Ge)₂Co₂(CO)₆ + H₂ + CO In the reactions of the polygermanes; Me₃GeGeH₃, Me₃SiGeH₃, Ge₂H₆, Ge₃H₈ and (GeH₃)₂SiMe₂ with Co₂(CO)₈, the M'-Ge, (M' = Si or Ge) bonds were quantitatively cleaved, and the new compound Ge₂Co₆(CO)₂₀, was isolated. This compound is assigned the structure: on spectroscopic evidence. Me₂GeH₂ also replaces a bridging CO group in the germanium - cobalt carbonyl species, to produce the new compounds; Me₂Ge₂Co₄(CO)₁₃ and (Me₂Ge)₂Ge₂Co₆(CO)₁₈. An X-ray crystallographic study on Me₂Ge₂Co₄(CO)₁₃ although showing the: skeleton, failed to refine properly. The reactions of Me₂SiH₂ and Me₂SnH₂ with germanium - cobalt carbonyl species failed to give a similar result. MeGeH₃ and GeCo₄(Co)₁₄ produced initially the analogous Me(H)Ge₂Co₄(CO)₁₃. However when left for 6 months, an unexpected rearrangement yielded (MeGe)₂Co₄(CO)₁₁. X-ray crystallography showed an irregular square bipyramidal structure, containing 5-coordinated square pyramidal germanium. This is this first example of such a group IVB - transition metal cluster. The decarbonylation of Ge₂Co₆(CO)₂₀ yielded the new compound [(OC)₄CoGe]₂Co₄(CO)₁₁ : which was found by X-ray crystallography to have a similar square bipyramidal structure. The new tin hydrides; MeSnH₂Mn(CO)₅ and Me₂SnHMn(CO)₅, have been prepared by the established route : Me₍₃₋ₓ₎SnHₓCl + NaMn(CO)₅ → Me₍₃₋ₓ₎SnHₓMn(CO)₅ + NaCl (x = 1,2) and characterised spectroscopically."],"dc:format.checksum.md5":["5bdc1977f020a4b0930b5c005c474b43","e14202ab27e47ddb00d33097327ba050","27fc56b47ea9ef15266dad350b1d134c"],"dc:identifier.uri":["https://researchcommons.waikato.ac.nz/bitstreams/76eaaa91-89e2-4be9-a23e-ef17b85b83e7/download"],"dc:publisher.institution":["The University of Waikato"],"dc:relation.isreferencedby":["https://hdl.handle.net/10289/16237"],"dc:rights":["https://researchcommons.waikato.ac.nz/bitstreams/b109eeef-d4a8-4021-921f-966a2f426818/download","All items in Research Commons are provided for private study and research purposes and are protected by copyright with all rights reserved unless otherwise indicated."],"dc:title":["The reactions of group IVB hydrides with carbonyl complexes of cobalt and manganese"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T05:57:55Z"}