Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

The structurally precise Cu‐rich hydride nanoclusters PdCu₁₄H₂(dtc/dtp)₆(C≡CPh)₆] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters Cu₂₈H₁₅(S₂CNⁿBu₂)₁₂]⁺ or Cu₂₀H₁₁{S₂P(OⁱPr)₂}₉] with phenyl acetylene in the presence of Pd(PPh₃)₂Cl₂. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd⁰ and four Cu^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated PdH₂]^2? unit and its Cu₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.