Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

• DOI: 10.1021/acs.inorgchem.9b03501
• Publication Date: 2020-01-24T17:40:21Z
• Authors: Rhone P. Brocha S...; Guan-Rong Huang; Jian-Hong Liao; Tzu-Hao Chiu; Kiran Kumarvarma ...; Xiaoping Wang; Julien Cartron; Samia Kahlal; Jean-Yves Saillard; C. W. Liu
• Keywords: Trigonal crystal system; Coordination geometry

Structurally precise copper hydrides [Cu11H2{S2P(OiPr)2}6(C≡CR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido cluster [Cu20H11{S2P(OiPr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields significantly improved by direct synthesis [Cu(CH3CN)4](PF6), [NH4][S2P(OiPr)2], NaBH4, alkynes along NEt3 in THF. 1, 2, 3 fully characterized single-crystal X-ray diffraction, ESI-MS, multinuclear NMR spectroscopy. All three clustershave 11 atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, two inside Cu11 cage, position which was ascertained a neutron diffraction structure 1 co-crystallized [Cu7(H){S2P(OiPr)2}6] (4) cluster. Six dithiophosphate alkynyl ligands stabilize Cu11H2 core adopt pyramidal coordination mode. This mode is so far unprecedented for hydride. The 1H resonance frequency appears at 4.8 ppm, value further confirmed 2H spectroscopy deuteride derivatives [Cu11(D)2{S2P(OiPr)2}6(C≡CR)3]. A DFT investigation allows understanding bonding within this new type copper(I) hydrides.