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Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit
Author(s) -
Chakrahari Kiran Kumarvarma,
Silalahi Rhone P. Brocha,
Chiu TzuHao,
Wang Xiaoping,
Azrou Nadia,
Kahlal Samia,
Liu YuChiao,
Chiang MingHsi,
Saillard JeanYves,
Liu C. W.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814264
Subject(s) - bimetallic strip , hydride , chemistry , crystallography , nanoclusters , copper , palladium , icosahedral symmetry , single crystal , crystal structure , isopropyl , coordination geometry , catalysis , metal , molecule , medicinal chemistry , hydrogen bond , organic chemistry
The structurally precise Cu‐rich hydride nanoclusters [PdCu 14 H 2 (dtc/dtp) 6 (C≡CPh) 6 ] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu 28 H 15 (S 2 CN n Bu 2 ) 12 ] + or [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] with phenyl acetylene in the presence of Pd(PPh 3 ) 2 Cl 2 . 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 0 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 [PdH 2 ] 2− unit and its Cu 14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.