{"id":{"repo_id":"waikato-masters","oai_identifier":"oai:researchcommons.waikato.ac.nz:10289/18301"},"canonical_url":"https://search.dev.ndltd.org/etd/waikato-masters/oai:researchcommons.waikato.ac.nz:10289/18301","repository":{"repo_id":"waikato-masters","name":"University Waikato","base_url":"https://researchcommons.waikato.ac.nz/server/oai/request"},"display":{"title":"Aspects of group 14 element - transition metal cluster chemistry","abstract":"The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). Some reactions of [SiCo₉(CO)₂₁]²⁻ and [GeCo₅(CO)₁₆]⁻ have been investigated. With [Ph₃PAu]⁺, [SiCo₉(CO)₂₁]²⁻ yielded a species formulated as [SiCo₉(CO)₂₂]³⁻ (from infrared and FABS mass spectroscopy data). A [CCo₁₀(CO)₂₄]⁻ species was also detected by FABS mass spectroscopy. NO⁺ appeared to add on to [SiCo₉(CO)₂₁]²⁻ but the exact nature of this product is not known. Reactions with Cp₂Co, [BuNCAu]⁺ and H⁺ have also yielded products which have not been fully characterised. Treatment of [SiCo₉(CO)₂₁]²⁻ with [(MeCN)₄Cu]⁺ led to disintegration of the cluster. [GeCo₅(CO)₁₆]⁻ did not react with [Ph₃PAu]⁺ or [CpNi(CO)]₂, but with CpFe(CO)₂I yielded Co₄(CO)₁₂, CpFeCo(CO)₆ and [GeCo₇(CO)₂₀]⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). The electrochemistry of clusters containing trigonal pyrimidal and spiro μ₄-EM₄ groups has been investigated using cyclic voltammetry. LₙMECo₃(CO)₉ (E = Si, Ge; and MLₙ = Co(CO)₄, Mn(CO)₅) compounds undergo an electrochemically reversible one electron reduction process, conforming with what has been reported for YCCo₃ (CO)₉ compounds. [Ge₂Co₇(CO)₂₁]⁻ and [Ge₂Co₅Fe₂(CO₂₂]⁻ contain two EM₃ redox centres which appear to behave independently. Reduction of spiro- E[Fe₂(CO)₈]₂ clusters occurs via two routes leading to [(CO)₄FeEFe₃(CO)₁₀]⁻ (more important for Si and Ge) or [(CO)₈Fe₂]E[Fe(CO)₄]₂²⁻ (more important for Sn and Pb). The cobaltocene reduction of Si[Fe₂(CO)₈]₂ yielded [(CO)₄FeSiFe₃(CO)₁₀]⁻, characterised using infrared spectroscopy. The vibrational spectra of E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn), E[Co₂(CO)₇]₂ (E = Si, Ge) and (CO)₄CoECo₃(CO)₉ (E = Si, Ge) have been recorded and assigned where possible. For the E[Co₂(CO)₇]₂ systems a ‘double-Bor’ model, based on Bor’s analysis of (μ-E)₂M₂(CO)₆ compounds, provides a consistent assignment for the carbonyl vibrations.","abstract_html":"The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). Some reactions of [SiCo₉(CO)₂₁]²⁻ and [GeCo₅(CO)₁₆]⁻ have been investigated. With [Ph₃PAu]⁺, [SiCo₉(CO)₂₁]²⁻ yielded a species formulated as [SiCo₉(CO)₂₂]³⁻ (from infrared and FABS mass spectroscopy data). A [CCo₁₀(CO)₂₄]⁻ species was also detected by FABS mass spectroscopy. NO⁺ appeared to add on to [SiCo₉(CO)₂₁]²⁻ but the exact nature of this product is not known. Reactions with Cp₂Co, [BuNCAu]⁺ and H⁺ have also yielded products which have not been fully characterised. Treatment of [SiCo₉(CO)₂₁]²⁻ with [(MeCN)₄Cu]⁺ led to disintegration of the cluster. [GeCo₅(CO)₁₆]⁻ did not react with [Ph₃PAu]⁺ or [CpNi(CO)]₂, but with CpFe(CO)₂I yielded Co₄(CO)₁₂, CpFeCo(CO)₆ and [GeCo₇(CO)₂₀]⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). The electrochemistry of clusters containing trigonal pyrimidal and spiro μ₄-EM₄ groups has been investigated using cyclic voltammetry. LₙMECo₃(CO)₉ (E = Si, Ge; and MLₙ = Co(CO)₄, Mn(CO)₅) compounds undergo an electrochemically reversible one electron reduction process, conforming with what has been reported for YCCo₃ (CO)₉ compounds. [Ge₂Co₇(CO)₂₁]⁻ and [Ge₂Co₅Fe₂(CO₂₂]⁻ contain two EM₃ redox centres which appear to behave independently. Reduction of spiro- E[Fe₂(CO)₈]₂ clusters occurs via two routes leading to [(CO)₄FeEFe₃(CO)₁₀]⁻ (more important for Si and Ge) or [(CO)₈Fe₂]E[Fe(CO)₄]₂²⁻ (more important for Sn and Pb). The cobaltocene reduction of Si[Fe₂(CO)₈]₂ yielded [(CO)₄FeSiFe₃(CO)₁₀]⁻, characterised using infrared spectroscopy. The vibrational spectra of E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn), E[Co₂(CO)₇]₂ (E = Si, Ge) and (CO)₄CoECo₃(CO)₉ (E = Si, Ge) have been recorded and assigned where possible. For the E[Co₂(CO)₇]₂ systems a ‘double-Bor’ model, based on Bor’s analysis of (μ-E)₂M₂(CO)₆ compounds, provides a consistent assignment for the carbonyl vibrations.","abstract_has_math":false,"creators":["Barris, Glen Clifton"],"institution":"The University of Waikato","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Nicholson, Brian K.","Mackay, Kenneth M."],"committee_chairs":[],"committee_members":[],"year":1990,"date_issued":"1990","date_published":"1990","updated_at":"2026-07-24T05:57:46Z","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/ccba6c26-7136-4744-af44-c2ac8be8d03c/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":["Nicholson, Brian K.","Mackay, Kenneth M."]},{"key":"dc:creator","label":"Author","values":["Barris, Glen Clifton"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["1990"]},{"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/10289/18301"]},{"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/ccba6c26-7136-4744-af44-c2ac8be8d03c/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/87306026-c81d-4a8d-8cfb-f31b2664745d/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). Some reactions of [SiCo₉(CO)₂₁]²⁻ and [GeCo₅(CO)₁₆]⁻ have been investigated. With [Ph₃PAu]⁺, [SiCo₉(CO)₂₁]²⁻ yielded a species formulated as [SiCo₉(CO)₂₂]³⁻ (from infrared and FABS mass spectroscopy data). A [CCo₁₀(CO)₂₄]⁻ species was also detected by FABS mass spectroscopy. NO⁺ appeared to add on to [SiCo₉(CO)₂₁]²⁻ but the exact nature of this product is not known. Reactions with Cp₂Co, [BuNCAu]⁺ and H⁺ have also yielded products which have not been fully characterised. Treatment of [SiCo₉(CO)₂₁]²⁻ with [(MeCN)₄Cu]⁺ led to disintegration of the cluster. [GeCo₅(CO)₁₆]⁻ did not react with [Ph₃PAu]⁺ or [CpNi(CO)]₂, but with CpFe(CO)₂I yielded Co₄(CO)₁₂, CpFeCo(CO)₆ and [GeCo₇(CO)₂₀]⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). The electrochemistry of clusters containing trigonal pyrimidal and spiro μ₄-EM₄ groups has been investigated using cyclic voltammetry. LₙMECo₃(CO)₉ (E = Si, Ge; and MLₙ = Co(CO)₄, Mn(CO)₅) compounds undergo an electrochemically reversible one electron reduction process, conforming with what has been reported for YCCo₃ (CO)₉ compounds. [Ge₂Co₇(CO)₂₁]⁻ and [Ge₂Co₅Fe₂(CO₂₂]⁻ contain two EM₃ redox centres which appear to behave independently. Reduction of spiro- E[Fe₂(CO)₈]₂ clusters occurs via two routes leading to [(CO)₄FeEFe₃(CO)₁₀]⁻ (more important for Si and Ge) or [(CO)₈Fe₂]E[Fe(CO)₄]₂²⁻ (more important for Sn and Pb). The cobaltocene reduction of Si[Fe₂(CO)₈]₂ yielded [(CO)₄FeSiFe₃(CO)₁₀]⁻, characterised using infrared spectroscopy. The vibrational spectra of E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn), E[Co₂(CO)₇]₂ (E = Si, Ge) and (CO)₄CoECo₃(CO)₉ (E = Si, Ge) have been recorded and assigned where possible. For the E[Co₂(CO)₇]₂ systems a ‘double-Bor’ model, based on Bor’s analysis of (μ-E)₂M₂(CO)₆ compounds, provides a consistent assignment for the carbonyl vibrations."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["573acac09212cb02b35153864ef81a60","e14202ab27e47ddb00d33097327ba050","25c5d74cf0a025d894be96776910ee4c"]},{"key":"dc:title","label":"Title","values":["Aspects of group 14 element - transition metal cluster chemistry"]}]}],"canonical_facts":{"dc:contributor.advisor":["Nicholson, Brian K.","Mackay, Kenneth M."],"dc:creator":["Barris, Glen Clifton"],"dc:date.issued":["1990"],"dc:description.abstract":["The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). Some reactions of [SiCo₉(CO)₂₁]²⁻ and [GeCo₅(CO)₁₆]⁻ have been investigated. With [Ph₃PAu]⁺, [SiCo₉(CO)₂₁]²⁻ yielded a species formulated as [SiCo₉(CO)₂₂]³⁻ (from infrared and FABS mass spectroscopy data). A [CCo₁₀(CO)₂₄]⁻ species was also detected by FABS mass spectroscopy. NO⁺ appeared to add on to [SiCo₉(CO)₂₁]²⁻ but the exact nature of this product is not known. Reactions with Cp₂Co, [BuNCAu]⁺ and H⁺ have also yielded products which have not been fully characterised. Treatment of [SiCo₉(CO)₂₁]²⁻ with [(MeCN)₄Cu]⁺ led to disintegration of the cluster. [GeCo₅(CO)₁₆]⁻ did not react with [Ph₃PAu]⁺ or [CpNi(CO)]₂, but with CpFe(CO)₂I yielded Co₄(CO)₁₂, CpFeCo(CO)₆ and [GeCo₇(CO)₂₀]⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy). The electrochemistry of clusters containing trigonal pyrimidal and spiro μ₄-EM₄ groups has been investigated using cyclic voltammetry. LₙMECo₃(CO)₉ (E = Si, Ge; and MLₙ = Co(CO)₄, Mn(CO)₅) compounds undergo an electrochemically reversible one electron reduction process, conforming with what has been reported for YCCo₃ (CO)₉ compounds. [Ge₂Co₇(CO)₂₁]⁻ and [Ge₂Co₅Fe₂(CO₂₂]⁻ contain two EM₃ redox centres which appear to behave independently. Reduction of spiro- E[Fe₂(CO)₈]₂ clusters occurs via two routes leading to [(CO)₄FeEFe₃(CO)₁₀]⁻ (more important for Si and Ge) or [(CO)₈Fe₂]E[Fe(CO)₄]₂²⁻ (more important for Sn and Pb). The cobaltocene reduction of Si[Fe₂(CO)₈]₂ yielded [(CO)₄FeSiFe₃(CO)₁₀]⁻, characterised using infrared spectroscopy. The vibrational spectra of E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn), E[Co₂(CO)₇]₂ (E = Si, Ge) and (CO)₄CoECo₃(CO)₉ (E = Si, Ge) have been recorded and assigned where possible. For the E[Co₂(CO)₇]₂ systems a ‘double-Bor’ model, based on Bor’s analysis of (μ-E)₂M₂(CO)₆ compounds, provides a consistent assignment for the carbonyl vibrations."],"dc:format.checksum.md5":["573acac09212cb02b35153864ef81a60","e14202ab27e47ddb00d33097327ba050","25c5d74cf0a025d894be96776910ee4c"],"dc:identifier.uri":["https://researchcommons.waikato.ac.nz/bitstreams/87306026-c81d-4a8d-8cfb-f31b2664745d/download"],"dc:publisher.institution":["The University of Waikato"],"dc:relation.isreferencedby":["https://hdl.handle.net/10289/18301"],"dc:rights":["https://researchcommons.waikato.ac.nz/bitstreams/ccba6c26-7136-4744-af44-c2ac8be8d03c/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":["Aspects of group 14 element - transition metal cluster chemistry"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T05:57:46Z"}