Addition of the Vulcanisation Accelerator Di(pentamethylene) thiuram Tetrasulfide (PMTT) to Low and High Valent Molybdenum Centres

IF 3.7 2区化学 Q2 CHEMISTRY, APPLIED

Applied Organometallic Chemistry Pub Date : 2025-09-02 DOI:10.1002/aoc.70381

Jagodish C. Sarker, David Pugh, Graeme Hogarth

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Abstract

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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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）

研究了二（五亚甲基）四硫脲（PMTT）对低价和高价钼中心的反应性，并与已被广泛研究的二硫脲（TDS）的反应性进行了比较，并产生了潜在的新的单源前体（ssp）对纳米二硫化钼的反应性。在丙酮中加热两种当量的PMTT和Mo(CO)6，以中等产量生成Mo(V)络合物[Mo(S2)(S2CNC5H10)3](1)，结晶导致S2部分氧化，得到1和[Mo(S2O)(S2CNC5H10)3] （1- o）的混合物。[NH4]2[MoS4]与两种等效的PMTT在室温下反应生成Mo （VI）配合物[MoS(S2)(S2CNC5H10)2](2)。虽然O2对O2稳定，但2对水敏感，缓慢水解产生相应的氧化物[MoO(S2)(S2CNC5H10)2](3)，其已被晶体学表征。这两种反应与TDS在相同条件下生成的产物不同，钼中心在与PMTT反应时更容易氧化。我们推测可能的机制途径观察到的产品，并提出简单和高产的2形成使其成为一个潜在的有吸引力的SSP。

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来源期刊

Applied Organometallic Chemistry 化学-无机化学与核化学

CiteScore

7.80

自引率

10.30%

发文量

408

审稿时长

2.2 months

期刊介绍： 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.