Highly reactive copper-dihydride clusters, [Cu₁₅ (H)₂ (S₂ CNR₂ )₆ (C₂ Ph)₆ ](PF₆ ) {R = ⁿ Bu (1_H ), ⁿ Pr (2_H ), ⁱ Bu (3_H )}, are isolated during the reaction of [Cu₂₈ H₁₅ {S₂ CNⁿ Bu₂ }₁₂ ](PF₆ ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu₁₃ (S₂ CNR₂ )₆ (C₂ Ph)₄ ]⁺ . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH₃ CN)₄ ](PF₆ ), BH₄^- and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu₁₅ (D)₂ (S₂ CNR₂ )₆ (C₂ Ph)₆ ]⁺ , and a single-crystal neutron structure of 2_H . Structural characterization of 1_H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH₂ )^- unit. Reaction of 3_H with Au(I) salts yields a highly luminescent [AuCu₁₂ (S₂ CNⁱ Bu₂ )₆ (C₂ Ph)₄ ]⁺ cluster.

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