{"id":{"repo_id":"waikato-masters","oai_identifier":"oai:researchcommons.waikato.ac.nz:10289/17031"},"canonical_url":"https://search.dev.ndltd.org/etd/waikato-masters/oai:researchcommons.waikato.ac.nz:10289/17031","repository":{"repo_id":"waikato-masters","name":"University Waikato","base_url":"https://researchcommons.waikato.ac.nz/server/oai/request"},"display":{"title":"ESIMS targeted synthesis of novel {Pt2S2} derivatives","abstract":"Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring- opening reactions of several epoxides with the nucleophilic dinuclear PtII complexes [Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N - tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide, epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4], [Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)- (PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4]) were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu- clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X- ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals suitable for a single crystal XRD experiment were not obtained. Both styrene oxide and epibromohydrin underwent ring-opening when reacted with 1b and the respec- tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)- CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide 2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro- line resulted in ring-opening when reacted with 1a however the resulting deriva- tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo- propane did not undergo ring-opening when reacted with 1a. The more activated 2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re- i sulted in ring-opening when reacted with 1a resulting in the isolation of deriva- tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)- (PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het- eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single crystal XRD studies. 12 was found to have a carbanionic center and is proposed to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ- S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ- S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char- acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring- opening when reacted with 1a however only polymeric decomposition species were detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl- pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv- ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex- cellent leaving group and the reaction of 2 with excess bromide resulted in the isola- tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino- thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+ (38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)- ii (PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4]. 17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}- NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C, 31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy. 2 was reacted with selenourea resulting in the detection by ESIMS of the mixed- bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy- phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno- late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E- R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and 19[BF4] were isolated and structurally characterised with heteronuclear NMR spec- troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy- drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco- genides, and the reaction between 2 and hydrazine was found to result in [Pt2- (μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy","abstract_html":"Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring- opening reactions of several epoxides with the nucleophilic dinuclear PtII complexes [Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N - tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide, epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4], [Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)- (PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4]) were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu- clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X- ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals suitable for a single crystal XRD experiment were not obtained. Both styrene oxide and epibromohydrin underwent ring-opening when reacted with 1b and the respec- tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)- CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide 2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro- line resulted in ring-opening when reacted with 1a however the resulting deriva- tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo- propane did not undergo ring-opening when reacted with 1a. The more activated 2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re- i sulted in ring-opening when reacted with 1a resulting in the isolation of deriva- tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)- (PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het- eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single crystal XRD studies. 12 was found to have a carbanionic center and is proposed to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ- S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ- S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char- acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring- opening when reacted with 1a however only polymeric decomposition species were detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl- pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv- ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex- cellent leaving group and the reaction of 2 with excess bromide resulted in the isola- tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino- thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+ (38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)- ii (PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4]. 17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}- NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C, 31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy. 2 was reacted with selenourea resulting in the detection by ESIMS of the mixed- bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy- phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno- late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E- R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and 19[BF4] were isolated and structurally characterised with heteronuclear NMR spec- troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy- drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco- genides, and the reaction between 2 and hydrazine was found to result in [Pt2- (μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy","abstract_has_math":false,"creators":["Fortney-Zirker, Ryland"],"institution":"The University of Waikato","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Henderson, William","Saunders, Graham","Lane, Joseph"],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-10-18","date_published":"2024-10-18","updated_at":"2026-07-24T05:57:49Z","subjects":["Inorganic Chemistry","mass spectrometry","platinum","coordination chemistry"],"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/ddb4bc78-0426-47c9-b120-6bcf84ecb484/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":["Henderson, William","Saunders, Graham","Lane, Joseph"]},{"key":"dc:creator","label":"Author","values":["Fortney-Zirker, Ryland"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2024-10-18"]},{"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/10289/17031"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Inorganic Chemistry","mass spectrometry","platinum","coordination chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["https://researchcommons.waikato.ac.nz/bitstreams/ddb4bc78-0426-47c9-b120-6bcf84ecb484/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/08d9ef53-d527-40f2-8d53-8fb036f5ad16/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring- opening reactions of several epoxides with the nucleophilic dinuclear PtII complexes [Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N - tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide, epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4], [Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)- (PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4]) were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu- clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X- ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals suitable for a single crystal XRD experiment were not obtained. Both styrene oxide and epibromohydrin underwent ring-opening when reacted with 1b and the respec- tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)- CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide 2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro- line resulted in ring-opening when reacted with 1a however the resulting deriva- tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo- propane did not undergo ring-opening when reacted with 1a. The more activated 2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re- i sulted in ring-opening when reacted with 1a resulting in the isolation of deriva- tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)- (PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het- eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single crystal XRD studies. 12 was found to have a carbanionic center and is proposed to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ- S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ- S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char- acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring- opening when reacted with 1a however only polymeric decomposition species were detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl- pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv- ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex- cellent leaving group and the reaction of 2 with excess bromide resulted in the isola- tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino- thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+ (38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)- ii (PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4]. 17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}- NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C, 31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy. 2 was reacted with selenourea resulting in the detection by ESIMS of the mixed- bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy- phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno- late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E- R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and 19[BF4] were isolated and structurally characterised with heteronuclear NMR spec- troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy- drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco- genides, and the reaction between 2 and hydrazine was found to result in [Pt2- (μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy"]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["3eccd7cd89417eef6d326263eedded5a","e14202ab27e47ddb00d33097327ba050","0e545231f486ba995912a4d9264694c9"]},{"key":"dc:title","label":"Title","values":["ESIMS targeted synthesis of novel {Pt2S2} derivatives"]}]}],"canonical_facts":{"dc:contributor.advisor":["Henderson, William","Saunders, Graham","Lane, Joseph"],"dc:creator":["Fortney-Zirker, Ryland"],"dc:date.issued":["2024-10-18"],"dc:description.abstract":["Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring- opening reactions of several epoxides with the nucleophilic dinuclear PtII complexes [Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N - tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide, epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4], [Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)- (PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4]) were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu- clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X- ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals suitable for a single crystal XRD experiment were not obtained. Both styrene oxide and epibromohydrin underwent ring-opening when reacted with 1b and the respec- tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)- CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide 2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro- line resulted in ring-opening when reacted with 1a however the resulting deriva- tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo- propane did not undergo ring-opening when reacted with 1a. The more activated 2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re- i sulted in ring-opening when reacted with 1a resulting in the isolation of deriva- tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)- (PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het- eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single crystal XRD studies. 12 was found to have a carbanionic center and is proposed to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ- S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ- S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char- acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring- opening when reacted with 1a however only polymeric decomposition species were detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl- pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv- ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex- cellent leaving group and the reaction of 2 with excess bromide resulted in the isola- tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino- thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+ (38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)- ii (PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4]. 17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}- NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C, 31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy. 2 was reacted with selenourea resulting in the detection by ESIMS of the mixed- bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy- phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno- late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E- R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and 19[BF4] were isolated and structurally characterised with heteronuclear NMR spec- troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy- drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco- genides, and the reaction between 2 and hydrazine was found to result in [Pt2- (μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy"],"dc:format.checksum.md5":["3eccd7cd89417eef6d326263eedded5a","e14202ab27e47ddb00d33097327ba050","0e545231f486ba995912a4d9264694c9"],"dc:identifier.uri":["https://researchcommons.waikato.ac.nz/bitstreams/08d9ef53-d527-40f2-8d53-8fb036f5ad16/download"],"dc:publisher.institution":["The University of Waikato"],"dc:relation.isreferencedby":["https://hdl.handle.net/10289/17031"],"dc:rights":["https://researchcommons.waikato.ac.nz/bitstreams/ddb4bc78-0426-47c9-b120-6bcf84ecb484/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:subject":["Inorganic Chemistry","mass spectrometry","platinum","coordination chemistry"],"dc:title":["ESIMS targeted synthesis of novel {Pt2S2} derivatives"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T05:57:49Z"}