{"title":"在低价和高价钼中心添加硫化促进剂二（五亚甲基）硫脲四硫化（PMTT）","authors":"Jagodish C. Sarker, David Pugh, Graeme Hogarth","doi":"10.1002/aoc.70381","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>The reactivity of di(pentamethylene) thiuram tetrasulfide (PMTT) towards both low and high valent molybdenum centres has been investigated to compare with the well-studied reactivity of thiuram disulfides (TDS) and to generate potential new single source precursors (SSPs) to nanoscale MoS<sub>2</sub>. Heating two equivalents of PMTT and Mo(CO)<sub>6</sub> in acetone affords the Mo(V) complex [Mo(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>3</sub>] (<b>1</b>) in moderate yields, crystallisation leading to partial oxidation of the S<sub>2</sub> moiety to give a mixture of <b>1</b> and [Mo(S<sub>2</sub>O)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>3</sub>] (<b>1</b>-O). Reaction of [NH<sub>4</sub>]<sub>2</sub>[MoS<sub>4</sub>] and two equivalents of PMTT occurs at room temperature to afford the Mo (VI) complex [MoS(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>2</sub>] (<b>2</b>) in quantitative yields. While stable to O<sub>2</sub>, <b>2</b> is sensitive to water, slow hydrolysis yielding the corresponding oxide [MoO(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>2</sub>] (<b>3</b>) which has been crystallographically characterised. Both of these reactions give different products to those formed from TDS under similar conditions, the molybdenum centre being more oxidised in reactions with PMTT. We speculate on possible mechanistic pathways to the observed products and suggest that the simple and high yielding formation of <b>2</b> makes it a potentially attractive SSP.</p>\n </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7000,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Addition of the Vulcanisation Accelerator Di(pentamethylene) thiuram Tetrasulfide (PMTT) to Low and High Valent Molybdenum Centres\",\"authors\":\"Jagodish C. Sarker, David Pugh, Graeme Hogarth\",\"doi\":\"10.1002/aoc.70381\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>The reactivity of di(pentamethylene) thiuram tetrasulfide (PMTT) towards both low and high valent molybdenum centres has been investigated to compare with the well-studied reactivity of thiuram disulfides (TDS) and to generate potential new single source precursors (SSPs) to nanoscale MoS<sub>2</sub>. Heating two equivalents of PMTT and Mo(CO)<sub>6</sub> in acetone affords the Mo(V) complex [Mo(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>3</sub>] (<b>1</b>) in moderate yields, crystallisation leading to partial oxidation of the S<sub>2</sub> moiety to give a mixture of <b>1</b> and [Mo(S<sub>2</sub>O)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>3</sub>] (<b>1</b>-O). Reaction of [NH<sub>4</sub>]<sub>2</sub>[MoS<sub>4</sub>] and two equivalents of PMTT occurs at room temperature to afford the Mo (VI) complex [MoS(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>2</sub>] (<b>2</b>) in quantitative yields. While stable to O<sub>2</sub>, <b>2</b> is sensitive to water, slow hydrolysis yielding the corresponding oxide [MoO(S<sub>2</sub>)(S<sub>2</sub>CNC<sub>5</sub>H<sub>10</sub>)<sub>2</sub>] (<b>3</b>) which has been crystallographically characterised. Both of these reactions give different products to those formed from TDS under similar conditions, the molybdenum centre being more oxidised in reactions with PMTT. We speculate on possible mechanistic pathways to the observed products and suggest that the simple and high yielding formation of <b>2</b> makes it a potentially attractive SSP.</p>\\n </div>\",\"PeriodicalId\":8344,\"journal\":{\"name\":\"Applied Organometallic Chemistry\",\"volume\":\"39 10\",\"pages\":\"\"},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2025-09-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Organometallic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/aoc.70381\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/aoc.70381","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Addition of the Vulcanisation Accelerator Di(pentamethylene) thiuram Tetrasulfide (PMTT) to Low and High Valent Molybdenum Centres
The reactivity of di(pentamethylene) thiuram tetrasulfide (PMTT) towards both low and high valent molybdenum centres has been investigated to compare with the well-studied reactivity of thiuram disulfides (TDS) and to generate potential new single source precursors (SSPs) to nanoscale MoS2. Heating two equivalents of PMTT and Mo(CO)6 in acetone affords the Mo(V) complex [Mo(S2)(S2CNC5H10)3] (1) in moderate yields, crystallisation leading to partial oxidation of the S2 moiety to give a mixture of 1 and [Mo(S2O)(S2CNC5H10)3] (1-O). Reaction of [NH4]2[MoS4] and two equivalents of PMTT occurs at room temperature to afford the Mo (VI) complex [MoS(S2)(S2CNC5H10)2] (2) in quantitative yields. While stable to O2, 2 is sensitive to water, slow hydrolysis yielding the corresponding oxide [MoO(S2)(S2CNC5H10)2] (3) which has been crystallographically characterised. Both of these reactions give different products to those formed from TDS under similar conditions, the molybdenum centre being more oxidised in reactions with PMTT. We speculate on possible mechanistic pathways to the observed products and suggest that the simple and high yielding formation of 2 makes it a potentially attractive SSP.
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All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.
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