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 MoS 2 . Heating two equivalents of PMTT and Mo(CO) 6 in acetone affords the Mo(V) complex [Mo(S 2 )(S 2 CNC 5 H 10 ) 3 ] ( 1 ) in moderate yields, crystallisation leading to partial oxidation of the S 2 moiety to give a mixture of 1 and [Mo(S 2 O)(S 2 CNC 5 H 10 ) 3 ] ( 1 ‐O). Reaction of [NH 4 ] 2 [MoS 4 ] and two equivalents of PMTT occurs at room temperature to afford the Mo (VI) complex [MoS(S 2 )(S 2 CNC 5 H 10 ) 2 ] ( 2 ) in quantitative yields. While stable to O 2 , 2 is sensitive to water, slow hydrolysis yielding the corresponding oxide [MoO(S 2 )(S 2 CNC 5 H 10 ) 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.