Publication | Open Access
Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit
56
Citations
45
References
2019
Year
The structurally precise Cu-rich hydride nanoclusters [PdCu<sub>14</sub> H<sub>2</sub> (dtc/dtp)<sub>6</sub> (C≡CPh)<sub>6</sub> ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu<sub>28</sub> H<sub>15</sub> (S<sub>2</sub> CN<sup>n</sup> Bu<sub>2</sub> )<sub>12</sub> ]<sup>+</sup> or [Cu<sub>20</sub> H<sub>11</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>9</sub> ] with phenyl acetylene in the presence of Pd(PPh<sub>3</sub> )<sub>2</sub> Cl<sub>2</sub> . 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 Pd<sup>0</sup> and four Cu<sup>I</sup> 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 [PdH<sub>2</sub> ]<sup>2-</sup> unit and its Cu<sub>14</sub> bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.
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