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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

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 (SNS)
Sponsoring Organization:
USDOE; Ministry of science and Technology of Taiwan
Grant/Contract Number:
AC05-00OR22725; 103-2113-M-259-003; 103-2739-M-213-001-MY3
OSTI ID:
1261479
Journal Information:
Angewandte Chemie (International Edition), Vol. 54, Issue 46; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 89 works
Citation information provided by
Web of Science

References (75)

Electron Transfer from Hexameric Copper Hydrides journal November 2013
Early transition metal hydride complexes: synthesis and reactivity journal November 2002
Ultrasensitive solution-cast quantum dot photodetectors journal July 2006
Controlled Growth of Gold Nanoparticles during Ligand Exchange journal February 1999
High capacity hydrogenstorage materials: attributes for automotive applications and techniques for materials discovery journal January 2010
Interstaple Dithiol Cross-Linking in Au 25 (SR) 18 Nanomolecules: A Combined Mass Spectrometric and Computational Study journal December 2011
Copper-catalysed selective hydroamination reactions of alkynes journal December 2014
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball journal May 2014
A unified view of ligand-protected gold clusters as superatom complexes journal July 2008
CuH in Asymmetric Reductions book January 2014
Facile Self-Assembly Synthesis and Characterization of Diselenophosphinato Octanuclear Cu I Clusters Inscribed in a Twelve-Vertex Selenium Polyhedron journal August 2012
Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters journal October 2014
Highly Diastereo- and Enantioselective CuH-Catalyzed Synthesis of 2,3-Disubstituted Indolines journal April 2015
Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H2Rh13(CO)24]3- journal February 1997
Die enantioselektive CuH-katalysierte 1,2-Reduktion von α,β-ungesättigten Ketonen journal October 2010
The Monolayer Thickness Dependence of Quantized Double-Layer Capacitances of Monolayer-Protected Gold Clusters journal September 1999
Iron-Catalyzed Hydrogenation, Hydride Transfer, and Hydrosilylation: An Alternative to Precious-Metal Complexes? journal June 2008
Hydrido Copper Clusters Supported by Dithiocarbamates: Oxidative Hydride Removal and Neutron Diffraction Analysis of [Cu 7 (H){S 2 C(aza-15-crown-5)} 6 ] journal June 2012
A Chiral Gold Nanocluster Au 20 Protected by Tetradentate Phosphine Ligands journal February 2014
Neutron diffraction structure analysis of a hexanuclear copper hydrido complex, H6Cu6[P(p-tolyl)3]6: an unexpected finding journal April 1989
CuH-Catalyzed Enantioselective 1,2-Reductions of α,β-Unsaturated Ketones journal June 2010
Synthesis and Characterization of a Cu 14 Hydride Cluster Supported by Neutral Donor Ligands journal February 2015
Der intermetalloide Cluster [(Cp*AlCu) 6 H 4 ], Stabilisierung eines Cu 6 -Kerns in einer oktaedrischen Al 6 -Hülle: molekulare Modellverbindungen für Hume-Rothery-Nanophasen journal June 2014
Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines journal August 2013
Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C5Me4SiMe3)LnH2” Units: A New Frontier in Rare Earth Metal Hydride Chemistry journal June 2007
CuH-Catalyzed Reactions journal August 2008
Large-Scale Synthesis of Thiolated Au 25 Clusters via Ligand Exchange Reactions of Phosphine-Stabilized Au 11 Clusters journal October 2005
Ligand-exchange synthesis of selenophenolate-capped Au25 nanoclusters journal January 2012
Surface Plasmon Spectroscopy of Nanosized Metal Particles journal January 1996
[Cu 32 (H) 20 {S 2 P(O i Pr) 2 } 12 ]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction journal April 2015
A DNA-based method for rationally assembling nanoparticles into macroscopic materials journal August 1996
Activation of Organic Substrates on Multi-Metallic Sites of Transition Metal Polyhydride Clusters Having C5Me5 Groups as Auxiliary Ligands journal May 2002
Change of Direction: Enantioselective CuH-Catalyzed 1,2-Reduction of α,β-Unsaturated Ketones journal October 2010
Bonding and Reactivity of a μ-Hydrido Dicopper Cation journal October 2013
Fundamentals of H 2 Binding and Reactivity on Transition Metals Underlying Hydrogenase Function and H 2 Production and Storage journal October 2007
Shape Modulation of Octanuclear Cu(I) or Ag(I) Dichalcogeno Template Clusters with Respect to the Nature of their Encapsulated Anions: A Combined Theoretical and Experimental Investigation journal June 2013
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate journal January 1984
Neutron Diffraction Studies of a Four-Coordinated Hydride in Near Square-Planar Geometry journal September 2014
Structural Basis for Ligand Exchange on Au 25 (SR) 18 journal June 2014
Dihydrogen Complexes as Homogeneous Reduction Catalysts journal April 1998
Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of 1,1-Disubstituted Alkenes journal October 2014
Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines journal August 2013
Anion Encapsulation and Geometric Changes in Hepta- and Hexanuclear Copper(I) Dichalcogeno Clusters: A Theoretical and Experimental Investigation journal October 2013
A Copper(I) Homocubane Collapses to a Tetracapped Tetrahedron Upon Hydride Insertion journal September 2011
A Chiral Gold Nanocluster Au 20 Protected by Tetradentate Phosphine Ligands journal February 2014
New approaches to hydrogen storage journal January 2009
Characterization of the Hydrides in Stryker’s Reagent: [HCu{P(C 6 H 5 ) 3 }] 6 journal February 2014
Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu I 8 Cage Inscribed in a S 12 Icosahedral Framework journal May 2009
Non-metallocene hydride complexes of the rare-earth metals journal August 2008
The Intermetalloid Cluster [(Cp*AlCu) 6 H 4 ], Embedding a Cu 6 Core Inside an Octahedral Al 6 Shell: Molecular Models of Hume-Rothery Nanophases journal June 2014
Facile Insertion of Carbon Dioxide into Cu 2 (μ-H) Dinuclear Units Supported by Tetraphosphine Ligands journal September 2014
A Nanospheric Polyhydrido Copper Cluster of Elongated Triangular Orthobicupola Array: Liberation of H 2 from Solar Energy journal March 2013
Copper-Catalyzed Hydrodefluorination of Fluoroarenes by Copper Hydride Intermediates journal February 2013
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball journal May 2014
Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements journal October 1997
Mass Spectrometry of Ligand Exchange Chelation of the Nanoparticle [Au 25 (SCH 2 CH 2 C 6 H 5 ) 18 ] 1− by CH 3 C 6 H 3 (SH) 2 journal December 2010
Surface ligands in synthesis, modification, assembly and biomedical applications of nanoparticles journal August 2014
Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus Selenolate journal September 2012
Selective hydride-mediated conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds using [(Ph3P)CuH]6 journal January 1988
Bonding and Reactivity of a μ-Hydrido Dicopper Cation journal October 2013
LiCa 3 As 2 H and Ca 14 As 6 X 7 (X = C, H, N): Two New Arsenide Hydride Phases Grown from Ca/Li Metal Flux journal September 2014
Synthesis of selenolate-protected Au18(SeC6H5)14 nanoclusters journal January 2013
Selenolate-Protected Au 38 Nanoclusters: Isolation and Structural Characterization journal September 2013
Recent advances in the coordination chemistry of diselenophosphates and allied ligands journal January 2007
Structural and Theoretical Basis for Ligand Exchange on Thiolate Monolayer Protected Gold Nanoclusters journal August 2012
Hydrogen at the flick of a switch journal September 2006
Octanuclear Copper(I) Clusters Inscribed in a Se 12 Icosahedron: Anion-Induced Modulation of the Core Size and Symmetry journal August 2009
Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals journal September 2011
Encapsulating Hydrides and Main-Group Anions in d10-Metal Clusters Stabilized by 1,1-Dichalcogeno Ligands journal December 2013
A Versatile Strategy for Quantum Dot Ligand Exchange journal January 2007
Thiol Ligand-Induced Transformation of Au 38 (SC 2 H 4 Ph) 24 to Au 36 (SPh- t -Bu) 24 journal June 2013
Copper-Catalyzed Hydrodefluorination of Fluoroarenes by Copper Hydride Intermediates journal February 2013
Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters journal October 2014
Fundamentals of H2 Binding and Reactivity on Transition Metals Underlying Hydrogenase Function and H2 Production and Storage journal December 2007
Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C 5 Me 4 SiMe 3 )LnH 2 ” Units: A New Frontier in Rare Earth Metal Hydride Chemistry journal June 2007

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[Cu 13 {S 2 CN n Bu 2 } 6 (acetylide) 4 ] + : A Two-Electron Superatom journal October 2016
Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit journal March 2019
[Ag 20 {S 2 P(OR) 2 } 12 ]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism journal June 2016
High-Nuclear Organometallic Copper(I)-Alkynide Clusters: Thermochromic Near-Infrared Luminescence and Solution Stability journal October 2016
A Fluxional Cu 8 H 6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO 2 journal May 2017
Synthesis and X-Ray Crystallographic Characterisation of Frustum-Shaped Ligated [Cu 18 H 16 (DPPE) 6 ] 2+ and [Cu 16 H 14 (DPPA) 6 ] 2+ Nanoclusters and Studies on Their H 2 Evolution Reactions journal January 2018
Hexadecanuclear Copper Monothiocarbonates: An Emissive Cluster Building Block: Hexadecanuclear Copper Monothiocarbonates: An Emissive Cluster Building Block journal April 2017
Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal January 2019
Synthesis, Structural Characterization, and H 2 Evolution Study of a Spheroid-Shape Hydride-Rich Copper Nanocluster journal March 2018
Metal Nanoclusters Stabilized by Selenol Ligands journal September 2019
A Tetradecanuclear Organometallic Copper(I)-Alkynide Cluster: Synthesis, Crystal Structure, and Luminescent Property journal June 2018
Thermochromic Luminescent Materials and Multi-Emission Bands in d10 Clusters journal March 2017
Copper hydride clusters in energy storage and conversion journal January 2019
Sub-nanometer Cu( i ) clusters: coordination-modulated (Se vs . S) atom-packing mode and emission journal January 2019
Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit journal March 2019

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Related Subjects

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