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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

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.
Authors:
 [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)
Publication Date:
OSTI Identifier:
1261479
Grant/Contract Number:
AC05-00OR22725;103-2113-M-259-003; 103-2739-M-213-001-MY3
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 46; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source
Sponsoring Org:
USDOE; Ministry of science and Technology of Taiwan
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY copper; density functional calculations; hydrides; intrinsic chirality; neutron diffraction; NEUTRON-DIFFRACTION ANALYSIS; PROTECTED GOLD CLUSTERS; LIGAND-EXCHANGE; RARE-EARTH; TRANSITION-METALS; HYDRIDE COMPLEXES; DONOR LIGANDS; NANOPARTICLES; SELENOLATE