Unusual core engineering on a copper hydride nanoball

A neutral polyhydrido copper cluster, [Cu₂₇H₁₅{S₂CNBu₂}₁₂] (abbreviated as [Cu₂₇H₁₅]), was prepared by the reaction of dithiocarbamates (dtc), Cu(I) salts and NaBH₄. The isolated cluster provides insights into core engineering, demonstrating its novel ability to reversibly add or remove one copper atom from the cluster core. Single-crystal X-ray analysis reveals that the new core-shell structure exhibits a Cu₂₄ rhombicuboctahedral outer cage and an inner Cu₃ triangular kernel. The two core-shell clusters, [Cu₂₇H₁₅{S₂CNBu₂}₁₂] and previously published [Cu₂₈H₁₅(S₂CNBu₂)₁₂]⁺ (abbreviated as [Cu₂₈H₁₅]⁺), are only differentiated by one copper atom in their inner core. Importantly, we demonstrate core engineering with the controllable reversible transition between an irregular Cu₄ tetrahedron and a Cu₃ triangle, whilst maintaining their outer Cu₂₄ shell intact. The 15 hydride atoms in [Cu₂₇H₁₅], coordinated in three different modes, are co-incident with the hydride positions in [Cu₂₈H₁₅]⁺. The degradation of [Cu₂₇H₁₅] in solution or the addition of one eq. of Cu(I) ions leads to the conversion of [Cu₂₇H₁₅] into [Cu₂₈H₁₅]⁺, while the reverse transformation can be achieved by the addition of either formic acid or a reducing agent to [Cu₂₈H₁₅]⁺. A dicationic species was observed in the ESI mass spectrum, and the composition is formulated as [Cu₅₆H₃₀(S₂CNBu₂)₂₄]²⁺, a dimer of [Cu₂₇H₁₅(S₂CNBu₂)₁₂ + Cu⁺]₂²⁺. The dimeric species was further explored by DFT calculations, suggesting that the lowest energy structure consists of a [Cu₂₈H₁₅]⁺ and a [Cu₂₇H₁₅] cluster connected through one Cu⁺ atom bridge. As a result, [Cu₂₇H₁₅] is considered an intermediate species in the formation of the more stable [Cu₂₈H₁₅]⁺ nanoball.