Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters
Dr. Rhone P. Brocha Silalahi
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorDr. Qi Wang
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorDr. Jian-Hong Liao
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorTzu-Hao Chiu
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorDr. Ying-Yann Wu
Institute of Chemistry, Academia Sinica, Taipei, 11528 Taiwan, R.O.C.
Search for more papers by this authorDr. Xiaoping Wang
Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831 USA
Search for more papers by this authorDr. Samia Kahlal
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorCorresponding Author
Prof. Dr. Jean-Yves Saillard
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorCorresponding Author
Prof. Dr. C. W. Liu
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorDr. Rhone P. Brocha Silalahi
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorDr. Qi Wang
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorDr. Jian-Hong Liao
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorTzu-Hao Chiu
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorDr. Ying-Yann Wu
Institute of Chemistry, Academia Sinica, Taipei, 11528 Taiwan, R.O.C.
Search for more papers by this authorDr. Xiaoping Wang
Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831 USA
Search for more papers by this authorDr. Samia Kahlal
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorCorresponding Author
Prof. Dr. Jean-Yves Saillard
Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France
Search for more papers by this authorCorresponding Author
Prof. Dr. C. W. Liu
Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 974301 Taiwan, R.O.C.
Search for more papers by this authorGraphical Abstract
While the reaction of the [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] template with Cu+ or Ag+ produces Cu12H2 and AgCu14H2 species in which the hydrides behave as Lewis bases, in the reaction with Au+, the hydrides act as reducing agents, leading to a luminescent, two-electron Au@Cu11 superatom, whose metal core has a defect fcc structure.
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.
Conflict of interest
The authors declare no conflict of interest.
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| anie202113266-sup-0001-SI.xyz25 KB | Supporting Information |
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