Diselenophosphate‐Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster |
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| Authors: | Dr Rajendra S Dhayal Jian‐Hong Liao Dr Xiaoping Wang Dr Yu‐Chiao Liu Dr Ming‐His Chiang Dr Samia Kahlal Prof Jean‐Yves Saillard Prof C W Liu |
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| Affiliation: | 1. 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;2. Centre for Chemical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda‐151 001 (India);3. Chemical and Engineering Materials Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge 37831 (USA);4. Institute of Chemistry, Academica Sinica, Taipei, 115 (Taiwan R.O.C.);5. UMR‐CNRS, 6226 “Institut des Sciences Chimiques de Rennes”, Université de Rennes 1, 35042 Rennes Cedex (France) |
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| 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 C3h 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. |
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| Keywords: | copper density functional calculations hydrides intrinsic chirality neutron diffraction |
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