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Irradiation at 460 nm of [Mo3(μ3-S)(μ2-S2)3(S2CNR2)3]I ([2a]I, R = Me; [2b]I, R = Et; [2c]I, R = iBu; [2d]I, R = CH2C6H5) in a mixed aqueous-polar organic medium with [Ru(bipy)3]2+ as photosensitizer and Et3N as electron donor leads to H2 evolution. Maximum activity (300 turnovers, 3 h) is found with R = iBu in 1:9 H2O:MeCN; diminished activity is attributed to deterioration of [Ru(bipy)3]2+. Monitoring of the photolysis mixture by mass spectrometry suggests transformation of [Mo3(μ3-S)(μ2-S2)3(S2CNR2)3]+ to [Mo3(μ3-S)(μ2-S)3(S2CNR2)3]+ via extrusion of sulfur on a time scale of minutes without accumulation of the intermediate [Mo3S6(S2CNR2)3]+ or [Mo3S5(S2CNR2)3]+ species. Deliberate preparation of [Mo3S4(S2CNEt2)3]+ ([3]+) and treatment with Et2NCS21- yields [Mo3S4(S2CNEt2)4] (4), where the fourth dithiocarbamate ligand bridges one edge of the Mo3 triangle. Photolysis of 4 leads to H2 evolution but at ∼25% the level observed for [Mo3S7(S2CNEt2)3]+. Early time monitoring of the photolyses shows that [Mo3S4(S2CNEt2)4] evolves H2 immediately and at constant rate, while [Mo3S7(S2CNEt2)3]+ shows a distinctive incubation prior to a more rapid H2 evolution rate. This observation implies the operation of catalysts of different identity in the two cases. Photolysis solutions of [Mo3S7(S2CNiBu2)3]+ left undisturbed over 24 h deposit the asymmetric Mo6 cluster [(iBu2NCS2)3(μ2-S2)2(μ3-S)Mo3](μ3-S)(μ3-η2,η1-S',η1-S″-S2)[Mo3(μ2-S)3(μ3-S)(S2CNiBu2)2(μ2-S2CNiBu2)] in crystalline form, suggesting that species with this hexametallic composition and core topology are the probable H2-evolving catalysts in photolyses beginning with [Mo3S7(S2CNR2)3]+. When used as solvent, N,N-dimethylformamide (DMF) suppresses H2-evolution but to a greater degree for [Mo3S4(S2CNEt2)4] than for [Mo3S7(S2CNEt2)3]+. Recrystallization of [Mo3S4(S2CNEt2)4] from DMF affords [Mo3S4(S2CNEt2)4(η1,κO-DMF)] (5), implying that inhibition by DMF arises from competition for a Mo coordination site that is requisite for H2 evolution. Computational assessment of [Mo3S4(S2CNMe2)3]+ following addition of 2H+ and 2e- suggests a Mo(H)-μ2(SH) intermediate as the lowest energy species for H2 elimination. An analogous pathway may be available to the Mo6 cluster via dissociation of one end of the μ2-S2CNR2 ligand, a known hemilabile ligand type, in the [Mo3S4]4+ fragment.

Irradiation at 460 nm of [Mo