Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters

Rhone P.Brocha Silalahi, Qi Wang, Jian Hong Liao, Tzu Hao Chiu, Ying Yann Wu, Xiaoping Wang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

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28 Scopus citations

Abstract

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu11]10+ metal core, making it a two-electron superatom.

Original languageEnglish
Article numbere202113266
JournalAngewandte Chemie - International Edition
Volume61
Issue number2
DOIs
StatePublished - Jan 10 2022

Funding

This work was supported by the Ministry of Science and Technology of Taiwan (MOST, Grant No. 109‐2113‐M‐259‐008), the France‐Taiwan ANR‐MOST program (project Nanoalloys) and the GENCI computing resource (grant A0090807367). Q.W. thanks the China Scholarship Council for a Ph.D. grant. The single‐crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work was supported by the Ministry of Science and Technology of Taiwan (MOST, Grant No. 109-2113-M-259-008), the France-Taiwan ANR-MOST program (project Nanoalloys) and the GENCI computing resource (grant A0090807367). Q.W. thanks the China Scholarship Council for a Ph.D. grant. The single-crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

FundersFunder number
ANR-MOST
France‐Taiwan ANR‐MOST program
Office of Science
Oak Ridge National Laboratory
China Scholarship Council
Ministry of Science and Technology, Taiwan109‐2113‐M‐259‐008
Grand Équipement National De Calcul IntensifA0090807367

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