Reactions of CS2 and C(S)NPh Adducts of N‐Heterocyclic Carbenes with [Ru3(CO)12]: Remarkable Reactivity of These Betaines Involving One or Two C–S Bond Activation Processes

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Abstract
Two structurally related tetranuclear complexes, [Ru4(μ4‐κ2C,S‐IMe–CS)(μ4‐S)(μ‐CO)2(CO)9] (1) and [Ru4(μ4‐κ2C,N‐TMe–CNPh)(μ4‐S)(μ‐CO)(CO)10] (2), have been isolated from reactions of [Ru3(CO)12] with 1 equiv. of the betaines IMe–CS2 (IMe = 1,3‐dimethylimidazol‐2‐ylidene) and TMe–C(S)NPh (TMe = 3‐methylthiazol‐2‐ylidene), respectively. Both products contain μ4‐S ligands that arise from the unprecedented cleavage of the thiocarbonyl C–S bonds of the corresponding betaines. A hexanuclear derivative, [Ru6{μ3‐κ4C2,N,S‐S(CH)2N(Me)CCNPh}2(μ4‐S)2(CO)14] (3), has also been obtained from the reaction involving TMe–C(S)NPh. This product arises not only from the cleavage of the betaine thiocarbonyl C–S bond, but also from the additional activation of the C–S bond within the thiazole ring.

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