The controlled generation of hydrogen sulfide (H₂S) under biologically relevant conditions is of paramount importance due to therapeutic interests. Via exploring the reactivity of a structurally characterized phenolate-bridged dinuclear zinc(II)-aqua complex {LZn^II(OH₂)}₂(ClO₄)₂ (1a) as a hydrolase model, we illustrate in this report that complex 1a readily hydrolyses CS₂ in the presence of Et₃N to afford H₂S. In contrast, penta-coordinated [Zn^II] sites in dinuclear {(LZn^II)₂(μ-X)}(ClO₄) complexes (7, X = OAc; 8, X = dimethylpyrazolyl) do not mediate CS₂ hydrolysis in the presence of externally added water and Et₃N presumably due to the unavailability of a coordination site for water at the [Zn^II] centers. Moreover, [Zn^II]-OH sites present in the isolated tetranuclear zinc(II) complex {(LZn^II)₂(μ-OH)}₂(ClO₄)₂ (4) react with CS₂, thereby suggesting that the [Zn^II]-OH site serves as the active nucleophile. Furthermore, mass spectrometric analyses on the reaction mixture consisting of 1a/Et₃N and CS₂ suggest the involvement of zinc(II)-thiocarbonate (3a) and COS species, thereby providing mechanistic insights into CS₂ hydrolysis mediated by the dinuclear [Zn^II] hydrolase model complex 1a.

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