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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

Abstract

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]
+ Show Author Affiliations
  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:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE; Ministry of science and Technology of Taiwan
OSTI Identifier:
1261479
Grant/Contract Number:  
AC05-00OR22725; 103-2113-M-259-003; 103-2739-M-213-001-MY3
Resource 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
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

Citation Formats

Dhayal, Rajendra S., Liao, Jian-Hong, Wang, Xiaoping, Liu, Yu-Chiao, Chiang, Ming-His, Kahlal, Samia, Saillard, Jean-Yves, and Liu, C. W. 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. United States: N. p., 2015. Web. doi:10.1002/anie.201506736.
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Dhayal, Rajendra S., Liao, Jian-Hong, Wang, Xiaoping, Liu, Yu-Chiao, Chiang, Ming-His, Kahlal, Samia, Saillard, Jean-Yves, & Liu, C. W. 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. United States. https://doi.org/10.1002/anie.201506736
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Dhayal, Rajendra S., Liao, Jian-Hong, Wang, Xiaoping, Liu, Yu-Chiao, Chiang, Ming-His, Kahlal, Samia, Saillard, Jean-Yves, and Liu, C. W. Mon . "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". United States. https://doi.org/10.1002/anie.201506736. https://www.osti.gov/servlets/purl/1261479.
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@article{osti_1261479,
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},
author = {Dhayal, Rajendra S. and Liao, Jian-Hong and Wang, Xiaoping and Liu, Yu-Chiao and Chiang, Ming-His and Kahlal, Samia and Saillard, Jean-Yves and Liu, C. W.},
abstractNote = {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.},
doi = {10.1002/anie.201506736},
journal = {Angewandte Chemie (International Edition)},
number = 46,
volume = 54,
place = {United States},
year = {Mon Nov 09 00:00:00 EST 2015},
month = {Mon Nov 09 00:00:00 EST 2015}
}
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    • Gautier, Romain; Latouche, Camille; Paris, Michael
    • Scientific Reports, Vol. 7, Issue 1
    • DOI: 10.1038/srep45537

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    journal, January 2019

    • Dhayal, Rajendra S.; van Zyl, Werner E.; Liu, C. W.
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    Sub-nanometer Cu( i ) clusters: coordination-modulated (Se vs . S) atom-packing mode and emission
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    • Ke, Feng; Song, Yongbo; Li, Hao
    • Dalton Transactions, Vol. 48, Issue 37
    • DOI: 10.1039/c9dt02908g

    Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit
    journal, March 2019

    • Chakrahari, Kiran Kumarvarma; Silalahi, Rhone P. Brocha; Chiu, Tzu‐Hao
    • Angewandte Chemie, Vol. 131, Issue 15
    • DOI: 10.1002/ange.201814264
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