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‐butyl dithiocarbamate (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 were supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single crystal neutron diffraction. Each hydride is connected to one Pd(0) and four Cu(I) atoms in slightly distorted trigonal bipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated PdH2 unit and its Cu14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.

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