Diselenophosphate‐Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster. (21st September 2015)

• Record Type: Journal Article
• Authors: Dhayal, Rajendra S.; Liao, Jian‐Hong; Wang, Xiaoping; Liu, Yu‐Chiao; Chiang, Ming‐His; Kahlal, Samia; Saillard, Jean‐Yves; Liu, C. W.
• Is Part Of: Angewandte Chemie. Volume 127:Number 46(2015)
• Page Start: 13808
• Page End: 13812
• Publication Date: 2015-09-21
• Subjects: Dichtefunktionalrechnungen -- Hydride -- Intrinsische Chiralität -- Kupfer -- Neutronenbeugung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201506736
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A polyhydrido copper nanocluster, [Cu20 H11 {Se2 P(O i Pr)2 }9 ] (2H ), which exhibits an intrinsically chiral inorganic core of C 3 symmetry, was synthesized from achiral [Cu20 H11 {S2 P(O i Pr)2 }9 ] (1H ) of C 3 h symmetry by a ligand‐exchange method. The structure has a distorted cuboctahedral Cu13 core, two triangular faces of which are capped along the C 3 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 of2H indicate that the chiral Cu20 H11 core retains its C 3 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 [Cu20 H11 (Se2 PH2 )9 ] (2H ′ ) as a simplified model.