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Article Dans Une Revue Angewandte Chemie International Edition Année : 2019

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

Résumé

The structurally precise Cu-rich hydride nanoclusters [PdCu H (dtc/dtp) (C≡CPh) ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu H (S CN Bu ) ] or [Cu H {S P(O Pr) } ] with phenyl acetylene in the presence of Pd(PPh ) Cl . 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 and four Cu 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 ] unit and its Cu bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.
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Dates et versions

hal-02087809 , version 1 (16-04-2019)

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Kiran Kumarvarma Chakrahari, Rhone P Brocha Silalahi, Tzu-Hao Chiu, Xiaoping Wang, Nadia Azrou, et al.. Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit. Angewandte Chemie International Edition, 2019, 58 (15), pp.4943-4947. ⟨10.1002/anie.201814264⟩. ⟨hal-02087809⟩
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