Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry
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Updated: Dec 30, 2025

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Rhone P Brocha Silalahi1, Guan-Rong Huang1, Jian-Hong Liao1
1Department of Chemistry , National Dong Hwa University , No. 1, Sec. 2, Da Hsueh Rd , Shoufeng , Hualien 97401 , Taiwan, R.O.C.
Abstract:
Structurally precise copper hydrides [Cu11H2{S2P(OPr)2}6(C≡CR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(OPr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH3CN)4](PF6), [NH4][S2P(OPr)2], NaBH4, and alkynes along with NEt3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu11 cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu7(H){S2P(OPr)2}6] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu11H2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by 2H NMR spectroscopy for their deuteride derivatives [Cu11(D)2{S2P(OPr)2}6(C≡CR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.
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