Title: Diselenophosphate-Induced Conversion of an Achiral [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] into a Chiral [Cu 20 H 11 {Se 2 P(O i Pr) 2 } 9 ] Polyhydrido Nanocluster

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [3];  [4];  [4];  [5];  [5];  [2]
  1. National Dong Hwa Univ., Hualien (Taiwan); Cenral Univ. of Punjab, Bathinda (India)
  2. National Dong Hwa Univ., Hualien (Taiwan)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Academia Sinica, Taipei (Taiwan)
  5. Univ. of Rennes (France)
+ Show Author Affiliations

A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)2}9] (2H), which exhibits an intrinsically chiral inorganic core of C-3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)2}9] (1(H)) of C-3h symmetry by a ligand-exchange method. Likewise, the structure has a distorted cuboctahedral Cu-13 core, two triangular faces of which are capped along the C-3 axis, one by a Cu-6 cupola and the other by a single Cu atom. The Cu-20 framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2(H) indicate that the chiral Cu20H11 core retains its C-3 symmetry in solution. Moreover, the 11 hydride ligands were located by neutron diffraction experiments and shown to be capping (3)-H and interstitial (5)-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)9] (2H') as a simplified model.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source
Sponsoring Organization:
Ministry of science and Technology of Taiwan; USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1261479
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 46 Vol. 54; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Copper hydride clusters in energy storage and conversion journal January 2019
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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