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Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit.
Chakrahari, Kiran Kumarvarma; Silalahi, Rhone P Brocha; Chiu, Tzu-Hao; Wang, Xiaoping; Azrou, Nadia; Kahlal, Samia; Liu, Yu-Chiao; Chiang, Ming-Hsi; Saillard, Jean-Yves; Liu, C W.
Afiliação
  • Chakrahari KK; Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan R.O.C.
  • Silalahi RPB; Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, 603203, India.
  • Chiu TH; Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan R.O.C.
  • Wang X; Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan R.O.C.
  • Azrou N; Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
  • Kahlal S; Univ Rennes, CNRS, ISCR-UMR 6226, 35000, Rennes, France.
  • Liu YC; Univ Rennes, CNRS, ISCR-UMR 6226, 35000, Rennes, France.
  • Chiang MH; Institute of Chemistry, Academia Sinica, Taipei, 11528, Taiwan R.O.C.
  • Saillard JY; Institute of Chemistry, Academia Sinica, Taipei, 11528, Taiwan R.O.C.
  • Liu CW; Univ Rennes, CNRS, ISCR-UMR 6226, 35000, Rennes, France.
Angew Chem Int Ed Engl ; 58(15): 4943-4947, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30770621
ABSTRACT
The structurally precise Cu-rich hydride nanoclusters [PdCu14 H2 (dtc/dtp)6 (C≡CPh)6 ] (dtc di-butyldithiocarbamate (1); dtp di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu28 H15 (S2 CNn Bu2 )12 ]+ or [Cu20 H11 {S2 P(Oi Pr)2 }9 ] with phenyl acetylene in the presence of Pd(PPh3 )2 Cl2 . 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 CuI 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.

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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Angew Chem Int Ed Engl Ano de publicação: 2019 Tipo de documento: Artigo