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ABSTRACT: An unprecedented air-stable, nanospheric polyhydrido copper cluster [Cu20(H)11(S2P(OiPr)2)9] (1H), which is the first example of elongated triangular orthobicupola copper atom array of C3h symmetry, was synthesized and characterized. Its composition is primarily determined by ESI mass spectrometry, and fully characterized by NMR (1H, 2H and 31P), and single crystal X-ray diffraction. The structure of complex 1H can be expressed by a trigonal-bipyramidal unit of [Cu2H5]3- anchored within an elongated triangular orthobicupola polyhedron of eighteen copper atoms, which is further stabilized by eighteen sulphur atoms from nine dithiophosphate ligands and six capping hydrides. The positions of eleven hydrides revealed from the low temperature X-ray diffraction was supported by a density functional theory (DFT) investigation on a simplified model [Cu20H11(S2PH2)9] of C3h symmetry. 1H is capable of releasing H2 gas under irradiation of sunlight, mild thermal condition (at 65 oC), or in the presence of acids at RT.
Journal of the American Chemical Society 03/2013; · 10.68 Impact Factor