{"id":{"repo_id":"waikato-masters","oai_identifier":"oai:researchcommons.waikato.ac.nz:10289/12766"},"canonical_url":"https://search.dev.ndltd.org/etd/waikato-masters/oai:researchcommons.waikato.ac.nz:10289/12766","repository":{"repo_id":"waikato-masters","name":"University Waikato","base_url":"https://researchcommons.waikato.ac.nz/server/oai/request"},"display":{"title":"Electrospray mass spectrometric analysis of transition metal carbonyl clusters","abstract":"A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4]. The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. A structure determination of [PPN][Mo(C0)3(ri5-CsHs)] is also reported.","abstract_html":"A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4]. The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. A structure determination of [PPN][Mo(C0)3(ri5-CsHs)] is also reported.","abstract_has_math":false,"creators":["Evans, Cameron"],"institution":"The University of Waikato","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Nicholson, Brian K.","Henderson, William","Mackay, Kenneth M."],"committee_chairs":[],"committee_members":[],"year":2002,"date_issued":"2002","date_published":"2002","updated_at":"2026-07-24T05:57:33Z","subjects":["Transition metal complexes Spectra","Metal crystals Spectra","Carbonyl compounds Spectra","Electrospray ionization mass spectrometry"],"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":[],"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.","Henderson, William","Mackay, Kenneth M."]},{"key":"dc:creator","label":"Author","values":["Evans, Cameron"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2002"]},{"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/10289/12766"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Transition metal complexes Spectra","Metal crystals Spectra","Carbonyl compounds Spectra","Electrospray ionization mass spectrometry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["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/7c795305-2038-4227-acd6-7042b62fcd07/download","https://researchcommons.waikato.ac.nz/bitstreams/1fe65557-96dd-4ce0-8b6a-1f5bbe86d465/download","https://researchcommons.waikato.ac.nz/bitstreams/25ca59a2-809b-4f62-a936-6823502b356f/download","https://researchcommons.waikato.ac.nz/bitstreams/03a57d87-c34b-4f2a-9e3f-20b7178582a0/download","https://researchcommons.waikato.ac.nz/bitstreams/3eeaeb21-ce0b-4b8b-bc04-2e74d529def1/download","https://researchcommons.waikato.ac.nz/bitstreams/b77bd9ce-4211-4ae0-84a0-9532eed39581/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4]. The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. A structure determination of [PPN][Mo(C0)3(ri5-CsHs)] is also reported."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["f86e388f6dfa3bf771f3213ba15e9535","2c2a472dd11300621cc13444d59e47cf","645d96197c816270ae583eb315cab10c","f5bd2d2c504acfe55b31574eb6a562fb","bb9feddf67747f741c7cf3e827c361ab","75dce08086288e7d0448eb7c048ce30e","f1c9cef8900b5756ac5ad21c393259de"]},{"key":"dc:title","label":"Title","values":["Electrospray mass spectrometric analysis of transition metal carbonyl clusters"]}]}],"canonical_facts":{"dc:contributor.advisor":["Nicholson, Brian K.","Henderson, William","Mackay, Kenneth M."],"dc:creator":["Evans, Cameron"],"dc:date.issued":["2002"],"dc:description.abstract":["A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4]. The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. 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