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

A polyhydrido copper nanocluster, [Cu 20 H 11 {Se 2 P(O i Pr) 2 } 9 ] ( 2 H ), which exhibits an intrinsically chiral inorganic core of C 3 symmetry, was synthesized from achiral [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] ( 1 H ) of C 3 h symmetry by a ligand‐exchange method. 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 Cu 20 H 11 core retains its C 3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ 3 ‐H and interstitial μ 5 ‐H ligands (in square‐pyramidal and trigonal‐bipyramidal cavities), as supported by DFT calculations on [Cu 20 H 11 (Se 2 PH 2 ) 9 ] ( 2 H ′ ) as a simplified model.