On the Critical Effect of the Metal (Mo vs. W) on the [3+2] Cycloaddition Reaction of M3S4 Clusters with Alkynes: Insights from Experiment and Theory

Whereas the cluster [Mo₃S₄(acac)₃(py)₃]⁺ ([ 1 ]⁺, acac=acetylacetonate, py=pyridine) reacts with a variety of alkynes, the cluster [W₃S₄(acac)₃(py)₃]⁺ ([ 2 ]⁺) remains unaffected under the same conditions. The reactions of cluster [ 1 ]⁺ show polyphasic kinetics, and in all cases clusters bearing a bridging dithiolene moiety are formed in the first step through the concerted [3+2] cycloaddition between the C?C atoms of the alkyne and a Mo(μ‐S)₂ moiety of the cluster. A computational study has been conducted to analyze the effect of the metal on these concerted [3+2] cycloaddition reactions. The calculations suggest that the reactions of cluster [ 2 ]⁺ with alkynes feature ΔG^≠ values only slightly larger than its molybdenum analogue, however, the differences in the reaction free energies between both metal clusters and the same alkyne reach up to approximately 10 kcal mol^?1, therefore indicating that the differences in the reactivity are essentially thermodynamic. The activation strain model (ASM) has been used to get more insights into the critical effect of the metal center in these cycloadditions, and the results reveal that the change in reactivity is entirely explained on the basis of the differences in the interaction energies E_int between the cluster and the alkyne. Further decomposition of the E_int values through the localized molecular orbital‐energy decomposition analysis (LMO‐EDA) indicates that substitution of the Mo atoms in cluster [ 1 ]⁺ by W induces changes in the electronic structure of the cluster that result in weaker intra‐ and inter‐fragment orbital interactions.