{"id":{"repo_id":"waikato-masters","oai_identifier":"oai:researchcommons.waikato.ac.nz:10289/18243"},"canonical_url":"https://search.dev.ndltd.org/etd/waikato-masters/oai:researchcommons.waikato.ac.nz:10289/18243","repository":{"repo_id":"waikato-masters","name":"University Waikato","base_url":"https://researchcommons.waikato.ac.nz/server/oai/request"},"display":{"title":"Some chemistry of Group IVB-cobalt carbonyl compounds","abstract":"The reaction of MeGeH₃ and Co₂(CO)₈ has been reinvestigated. Products obtained from this reaction include MeGeCo₃(CO)₁₁, Me₂Ge₂Co₄(CO)₁₄ (or [MeGeCo(CO)₄]₂Co₂(CO)₆), MeGeHCo₂(CO)ₓ (x = 7 or 8), (MeGe)₂Co₄(CO)₁₁ and Co₄(CO)₁₂, the relative proportion depending on the ratio of the reactants. Decarbonylation of a mixture of Me₂Ge₂Co₄(CO)₁₄, MeGeCo₃(CO)₁₁ and MeGeHCo₂(CO)ₓ produced a small amount of (MeGe)₂Co₄(CO)₁₁ together with a new compound Me₃Ge₃Co₅(CO)₁₄ (or (MeGe)₂Co₄(CO)₁₀(μ-Ge(Me)Co(CO)₄)) which was characterised by a full crystal structure. The crystal structure of MeGeCo₃(CO)₁₁ was also determined. A new, convenient and efficient route to (MeM')₂Co₄(CO)₁₁ (M'= Si, Ge) clusters has been developed, based on the reaction of MeM'H₃ with Co₄(CO)₁₂. Reactions of RGeH₃ (R= Me, Et, Ph) with M'Co₄(CO)₁₄ (M'= Si, Ge) have been investigated in detail. (RGeH)ₙGeCo₄(CO)₁₄₋ₙ (n= 1 or 2) were obtained from the GeCo₄(CO)₁₄ system. Further reaction of the products with Co₂(CO)₈ produced two new clusters : RGe₂Co₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(GeCo(CO)₄)) (R= Me, Ph) from the (RGeH)GeCo₄(CO)₁₃ reaction and R₂Ge₃Co₆(CO)₁₇ (or (RGe)₂Co₄(CO)₁₀(μ-GeCo₂(CO)₇) from the (RGeH)₂GeCo₄(CO)₁₂ reaction. Representative X-ray crystal structures of MeGe₂Co₅(CO)₁₅ and Et₂Ge₃Co₆(CO)₁₇ are described. With SiCo₄(CO)₁₄, MeGeH₃ produced a mixture of compounds, including the new compound RGeSiCo₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(SiCo(CO)₄), characterised by a full crystal structure), (RGe)₂Co₄(CO)₁₁, Me₃Ge₃Co₅(CO)₁₄, SiCo₄(CO)₁₃, Co₄(CO)₁₂ and Co₂(CO)₈. RR'GeH₂ (R= Me, R'=Me, Cl) reacted with GeCo₄(CO)₁₄ to form (RR'Ge)GeCo₄(CO)₁₃ and (RR'Ge)₂GeCo₄ (CO)₁₂ depending on the reaction conditions. Preliminary studies on the reaction of Me₂GeH₂ with SiCo₄(CO)₁₄ indicated that Me₂GeCo₂(CO)₇, Me₂GeCo₂(CO)₈ (Me₂Ge)₂Co₂(CO)₆ and SiCo₄(CO)₁₃ were formed. The reaction of MeSiH₃ with GeCo₄(CO)₁₄ resulted only in the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃. However, in the reaction of MeSiH₃ with SiCo₄(CO)₁₄, a number of products were formed. These include MeSiH₂Co(CO)₄, Co₂(CO)₈, SiCo₄(CO)₁₃ and a new product of formula MeSi₂Co₅(CO)₁₅ (or (MeSi)Co₄(CO)₁₁(SiCo(CO)₄). Preliminary studies on the following reactions were also carried out: the reaction of Me₂SiH₂ with M'Co₄(CO)₁₄ and the reaction of Me₂SiH₂ with Co₄(CO)₁₂. In the GeCo₄(CO)₁₄ system no reaction other than the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃ was observed. In both the SiCo₄(CO)₁₄ and Co₄(CO)₁₂ systems, Me₂SiHCo(CO)₄, Me₂[Co(CO)₄]SiOCCo₃(CO)₉, Co₂(CO)₈ and Co₄(CO)₁₂ were obtained. All new products in this study were fully characterised by infrared, ¹H NMR, ¹³CO NMR and mass spectroscopy, and for most, by X-ray crystallography. Some ¹³CO NMR studies on M'-Co carbonyl compounds are also reported.","abstract_html":"The reaction of MeGeH₃ and Co₂(CO)₈ has been reinvestigated. Products obtained from this reaction include MeGeCo₃(CO)₁₁, Me₂Ge₂Co₄(CO)₁₄ (or [MeGeCo(CO)₄]₂Co₂(CO)₆), MeGeHCo₂(CO)ₓ (x = 7 or 8), (MeGe)₂Co₄(CO)₁₁ and Co₄(CO)₁₂, the relative proportion depending on the ratio of the reactants. Decarbonylation of a mixture of Me₂Ge₂Co₄(CO)₁₄, MeGeCo₃(CO)₁₁ and MeGeHCo₂(CO)ₓ produced a small amount of (MeGe)₂Co₄(CO)₁₁ together with a new compound Me₃Ge₃Co₅(CO)₁₄ (or (MeGe)₂Co₄(CO)₁₀(μ-Ge(Me)Co(CO)₄)) which was characterised by a full crystal structure. The crystal structure of MeGeCo₃(CO)₁₁ was also determined. A new, convenient and efficient route to (MeM')₂Co₄(CO)₁₁ (M'= Si, Ge) clusters has been developed, based on the reaction of MeM'H₃ with Co₄(CO)₁₂. Reactions of RGeH₃ (R= Me, Et, Ph) with M'Co₄(CO)₁₄ (M'= Si, Ge) have been investigated in detail. (RGeH)ₙGeCo₄(CO)₁₄₋ₙ (n= 1 or 2) were obtained from the GeCo₄(CO)₁₄ system. Further reaction of the products with Co₂(CO)₈ produced two new clusters : RGe₂Co₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(GeCo(CO)₄)) (R= Me, Ph) from the (RGeH)GeCo₄(CO)₁₃ reaction and R₂Ge₃Co₆(CO)₁₇ (or (RGe)₂Co₄(CO)₁₀(μ-GeCo₂(CO)₇) from the (RGeH)₂GeCo₄(CO)₁₂ reaction. Representative X-ray crystal structures of MeGe₂Co₅(CO)₁₅ and Et₂Ge₃Co₆(CO)₁₇ are described. With SiCo₄(CO)₁₄, MeGeH₃ produced a mixture of compounds, including the new compound RGeSiCo₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(SiCo(CO)₄), characterised by a full crystal structure), (RGe)₂Co₄(CO)₁₁, Me₃Ge₃Co₅(CO)₁₄, SiCo₄(CO)₁₃, Co₄(CO)₁₂ and Co₂(CO)₈. RR'GeH₂ (R= Me, R'=Me, Cl) reacted with GeCo₄(CO)₁₄ to form (RR'Ge)GeCo₄(CO)₁₃ and (RR'Ge)₂GeCo₄ (CO)₁₂ depending on the reaction conditions. Preliminary studies on the reaction of Me₂GeH₂ with SiCo₄(CO)₁₄ indicated that Me₂GeCo₂(CO)₇, Me₂GeCo₂(CO)₈ (Me₂Ge)₂Co₂(CO)₆ and SiCo₄(CO)₁₃ were formed. The reaction of MeSiH₃ with GeCo₄(CO)₁₄ resulted only in the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃. However, in the reaction of MeSiH₃ with SiCo₄(CO)₁₄, a number of products were formed. These include MeSiH₂Co(CO)₄, Co₂(CO)₈, SiCo₄(CO)₁₃ and a new product of formula MeSi₂Co₅(CO)₁₅ (or (MeSi)Co₄(CO)₁₁(SiCo(CO)₄). Preliminary studies on the following reactions were also carried out: the reaction of Me₂SiH₂ with M'Co₄(CO)₁₄ and the reaction of Me₂SiH₂ with Co₄(CO)₁₂. In the GeCo₄(CO)₁₄ system no reaction other than the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃ was observed. In both the SiCo₄(CO)₁₄ and Co₄(CO)₁₂ systems, Me₂SiHCo(CO)₄, Me₂[Co(CO)₄]SiOCCo₃(CO)₉, Co₂(CO)₈ and Co₄(CO)₁₂ were obtained. All new products in this study were fully characterised by infrared, ¹H NMR, ¹³CO NMR and mass spectroscopy, and for most, by X-ray crystallography. Some ¹³CO NMR studies on M'-Co carbonyl compounds are also reported.","abstract_has_math":false,"creators":["Lee, Siew Kim"],"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":1988,"date_issued":"1988","date_published":"1988","updated_at":"2026-07-24T05:57:38Z","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/f2c40ebc-7c73-4d40-8f9f-bad0e3a6ad02/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":["Lee, Siew Kim"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["1988"]},{"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/10289/18243"]},{"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/f2c40ebc-7c73-4d40-8f9f-bad0e3a6ad02/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/e054a21e-2535-4368-b567-7b876df96577/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The reaction of MeGeH₃ and Co₂(CO)₈ has been reinvestigated. Products obtained from this reaction include MeGeCo₃(CO)₁₁, Me₂Ge₂Co₄(CO)₁₄ (or [MeGeCo(CO)₄]₂Co₂(CO)₆), MeGeHCo₂(CO)ₓ (x = 7 or 8), (MeGe)₂Co₄(CO)₁₁ and Co₄(CO)₁₂, the relative proportion depending on the ratio of the reactants. Decarbonylation of a mixture of Me₂Ge₂Co₄(CO)₁₄, MeGeCo₃(CO)₁₁ and MeGeHCo₂(CO)ₓ produced a small amount of (MeGe)₂Co₄(CO)₁₁ together with a new compound Me₃Ge₃Co₅(CO)₁₄ (or (MeGe)₂Co₄(CO)₁₀(μ-Ge(Me)Co(CO)₄)) which was characterised by a full crystal structure. The crystal structure of MeGeCo₃(CO)₁₁ was also determined. A new, convenient and efficient route to (MeM')₂Co₄(CO)₁₁ (M'= Si, Ge) clusters has been developed, based on the reaction of MeM'H₃ with Co₄(CO)₁₂. Reactions of RGeH₃ (R= Me, Et, Ph) with M'Co₄(CO)₁₄ (M'= Si, Ge) have been investigated in detail. (RGeH)ₙGeCo₄(CO)₁₄₋ₙ (n= 1 or 2) were obtained from the GeCo₄(CO)₁₄ system. Further reaction of the products with Co₂(CO)₈ produced two new clusters : RGe₂Co₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(GeCo(CO)₄)) (R= Me, Ph) from the (RGeH)GeCo₄(CO)₁₃ reaction and R₂Ge₃Co₆(CO)₁₇ (or (RGe)₂Co₄(CO)₁₀(μ-GeCo₂(CO)₇) from the (RGeH)₂GeCo₄(CO)₁₂ reaction. Representative X-ray crystal structures of MeGe₂Co₅(CO)₁₅ and Et₂Ge₃Co₆(CO)₁₇ are described. With SiCo₄(CO)₁₄, MeGeH₃ produced a mixture of compounds, including the new compound RGeSiCo₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(SiCo(CO)₄), characterised by a full crystal structure), (RGe)₂Co₄(CO)₁₁, Me₃Ge₃Co₅(CO)₁₄, SiCo₄(CO)₁₃, Co₄(CO)₁₂ and Co₂(CO)₈. RR'GeH₂ (R= Me, R'=Me, Cl) reacted with GeCo₄(CO)₁₄ to form (RR'Ge)GeCo₄(CO)₁₃ and (RR'Ge)₂GeCo₄ (CO)₁₂ depending on the reaction conditions. Preliminary studies on the reaction of Me₂GeH₂ with SiCo₄(CO)₁₄ indicated that Me₂GeCo₂(CO)₇, Me₂GeCo₂(CO)₈ (Me₂Ge)₂Co₂(CO)₆ and SiCo₄(CO)₁₃ were formed. The reaction of MeSiH₃ with GeCo₄(CO)₁₄ resulted only in the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃. However, in the reaction of MeSiH₃ with SiCo₄(CO)₁₄, a number of products were formed. These include MeSiH₂Co(CO)₄, Co₂(CO)₈, SiCo₄(CO)₁₃ and a new product of formula MeSi₂Co₅(CO)₁₅ (or (MeSi)Co₄(CO)₁₁(SiCo(CO)₄). Preliminary studies on the following reactions were also carried out: the reaction of Me₂SiH₂ with M'Co₄(CO)₁₄ and the reaction of Me₂SiH₂ with Co₄(CO)₁₂. In the GeCo₄(CO)₁₄ system no reaction other than the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃ was observed. In both the SiCo₄(CO)₁₄ and Co₄(CO)₁₂ systems, Me₂SiHCo(CO)₄, Me₂[Co(CO)₄]SiOCCo₃(CO)₉, Co₂(CO)₈ and Co₄(CO)₁₂ were obtained. All new products in this study were fully characterised by infrared, ¹H NMR, ¹³CO NMR and mass spectroscopy, and for most, by X-ray crystallography. Some ¹³CO NMR studies on M'-Co carbonyl compounds are also reported."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["8f8c3a8a2336b8f590df59df13e1db89","e14202ab27e47ddb00d33097327ba050","e5be314152ad6ca62aabe6fe7d96ec5c"]},{"key":"dc:title","label":"Title","values":["Some chemistry of Group IVB-cobalt carbonyl compounds"]}]}],"canonical_facts":{"dc:contributor.advisor":["Mackay, Kenneth M.","Nicholson, Brian K."],"dc:creator":["Lee, Siew Kim"],"dc:date.issued":["1988"],"dc:description.abstract":["The reaction of MeGeH₃ and Co₂(CO)₈ has been reinvestigated. Products obtained from this reaction include MeGeCo₃(CO)₁₁, Me₂Ge₂Co₄(CO)₁₄ (or [MeGeCo(CO)₄]₂Co₂(CO)₆), MeGeHCo₂(CO)ₓ (x = 7 or 8), (MeGe)₂Co₄(CO)₁₁ and Co₄(CO)₁₂, the relative proportion depending on the ratio of the reactants. Decarbonylation of a mixture of Me₂Ge₂Co₄(CO)₁₄, MeGeCo₃(CO)₁₁ and MeGeHCo₂(CO)ₓ produced a small amount of (MeGe)₂Co₄(CO)₁₁ together with a new compound Me₃Ge₃Co₅(CO)₁₄ (or (MeGe)₂Co₄(CO)₁₀(μ-Ge(Me)Co(CO)₄)) which was characterised by a full crystal structure. The crystal structure of MeGeCo₃(CO)₁₁ was also determined. A new, convenient and efficient route to (MeM')₂Co₄(CO)₁₁ (M'= Si, Ge) clusters has been developed, based on the reaction of MeM'H₃ with Co₄(CO)₁₂. Reactions of RGeH₃ (R= Me, Et, Ph) with M'Co₄(CO)₁₄ (M'= Si, Ge) have been investigated in detail. (RGeH)ₙGeCo₄(CO)₁₄₋ₙ (n= 1 or 2) were obtained from the GeCo₄(CO)₁₄ system. Further reaction of the products with Co₂(CO)₈ produced two new clusters : RGe₂Co₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(GeCo(CO)₄)) (R= Me, Ph) from the (RGeH)GeCo₄(CO)₁₃ reaction and R₂Ge₃Co₆(CO)₁₇ (or (RGe)₂Co₄(CO)₁₀(μ-GeCo₂(CO)₇) from the (RGeH)₂GeCo₄(CO)₁₂ reaction. Representative X-ray crystal structures of MeGe₂Co₅(CO)₁₅ and Et₂Ge₃Co₆(CO)₁₇ are described. With SiCo₄(CO)₁₄, MeGeH₃ produced a mixture of compounds, including the new compound RGeSiCo₅(CO)₁₅ (or (RGe)Co₄(CO)₁₁(SiCo(CO)₄), characterised by a full crystal structure), (RGe)₂Co₄(CO)₁₁, Me₃Ge₃Co₅(CO)₁₄, SiCo₄(CO)₁₃, Co₄(CO)₁₂ and Co₂(CO)₈. RR'GeH₂ (R= Me, R'=Me, Cl) reacted with GeCo₄(CO)₁₄ to form (RR'Ge)GeCo₄(CO)₁₃ and (RR'Ge)₂GeCo₄ (CO)₁₂ depending on the reaction conditions. Preliminary studies on the reaction of Me₂GeH₂ with SiCo₄(CO)₁₄ indicated that Me₂GeCo₂(CO)₇, Me₂GeCo₂(CO)₈ (Me₂Ge)₂Co₂(CO)₆ and SiCo₄(CO)₁₃ were formed. The reaction of MeSiH₃ with GeCo₄(CO)₁₄ resulted only in the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃. However, in the reaction of MeSiH₃ with SiCo₄(CO)₁₄, a number of products were formed. These include MeSiH₂Co(CO)₄, Co₂(CO)₈, SiCo₄(CO)₁₃ and a new product of formula MeSi₂Co₅(CO)₁₅ (or (MeSi)Co₄(CO)₁₁(SiCo(CO)₄). Preliminary studies on the following reactions were also carried out: the reaction of Me₂SiH₂ with M'Co₄(CO)₁₄ and the reaction of Me₂SiH₂ with Co₄(CO)₁₂. In the GeCo₄(CO)₁₄ system no reaction other than the decarbonylation of GeCo₄(CO)₁₄ to GeCo₄(CO)₁₃ was observed. In both the SiCo₄(CO)₁₄ and Co₄(CO)₁₂ systems, Me₂SiHCo(CO)₄, Me₂[Co(CO)₄]SiOCCo₃(CO)₉, Co₂(CO)₈ and Co₄(CO)₁₂ were obtained. All new products in this study were fully characterised by infrared, ¹H NMR, ¹³CO NMR and mass spectroscopy, and for most, by X-ray crystallography. Some ¹³CO NMR studies on M'-Co carbonyl compounds are also reported."],"dc:format.checksum.md5":["8f8c3a8a2336b8f590df59df13e1db89","e14202ab27e47ddb00d33097327ba050","e5be314152ad6ca62aabe6fe7d96ec5c"],"dc:identifier.uri":["https://researchcommons.waikato.ac.nz/bitstreams/e054a21e-2535-4368-b567-7b876df96577/download"],"dc:publisher.institution":["The University of Waikato"],"dc:relation.isreferencedby":["https://hdl.handle.net/10289/18243"],"dc:rights":["https://researchcommons.waikato.ac.nz/bitstreams/f2c40ebc-7c73-4d40-8f9f-bad0e3a6ad02/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":["Some chemistry of Group IVB-cobalt carbonyl compounds"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T05:57:38Z"}