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ESIMS targeted synthesis of novel {Pt2S2} derivatives Fortney-Zirker, Ryland Henderson, William Saunders, Graham Lane, Joseph 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 The University of Waikato 2024-10-18 Thesis en https://hdl.handle.net/10289/17031 https://researchcommons.waikato.ac.nz/bitstreams/08d9ef53-d527-40f2-8d53-8fb036f5ad16/download 3eccd7cd89417eef6d326263eedded5a https://researchcommons.waikato.ac.nz/bitstreams/ddb4bc78-0426-47c9-b120-6bcf84ecb484/download e14202ab27e47ddb00d33097327ba050 https://researchcommons.waikato.ac.nz/bitstreams/f1dd1719-6a03-4d04-a1f1-37f5c3b7dac8/download 0e545231f486ba995912a4d9264694c9 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. Inorganic Chemistry mass spectrometry platinum coordination chemistry