title: Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster.
abstract: A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)2}9] (2H), which exhibits an intrinsically chiral inorganic core of C3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)2}9] (1H) of C(3h) symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu13 core, two triangular faces of which are capped along the C3 axis, one by a Cu6 cupola and the other by a single Cu atom. The Cu20 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 2H indicate that the chiral Cu20H11 core retains its C3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ3-H and interstitial μ5-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)9] (2H') as a simplified model.
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Road, Shoufeng, Hualien 97401 (Taiwan R.O.C.) http://faculty.ndhu.edu.tw/∼cwl/index.htm.|Centre for Chemical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda-151 001 (India).
authors.forename: Rajendra S
authors.initials: RS
authors.lastname: Dhayal
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Road, Shoufeng, Hualien 97401 (Taiwan R.O.C.) http://faculty.ndhu.edu.tw/∼cwl/index.htm.
authors.forename: Jian-Hong
authors.initials: JH
authors.lastname: Liao
authors.affiliation: Chemical and Engineering Materials Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge 37831 (USA).
authors.forename: Xiaoping
authors.initials: X
authors.lastname: Wang
authors.affiliation: Institute of Chemistry, Academica Sinica, Taipei, 115 (Taiwan R.O.C.).
authors.forename: Yu-Chiao
authors.initials: YC
authors.lastname: Liu
authors.affiliation: Institute of Chemistry, Academica Sinica, Taipei, 115 (Taiwan R.O.C.).
authors.forename: Ming-His
authors.initials: MH
authors.lastname: Chiang
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1, 35042 Rennes Cedex (France).
authors.forename: Samia
authors.initials: S
authors.lastname: Kahlal
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1, 35042 Rennes Cedex (France).
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Saillard
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Road, Shoufeng, Hualien 97401 (Taiwan R.O.C.) http://faculty.ndhu.edu.tw/∼cwl/index.htm. chenwei@mail.ndhu.edu.tw.
authors.forename: C W
authors.initials: CW
authors.lastname: Liu
keywords: copper; density functional calculations; hydrides; intrinsic chirality; neutron diffraction