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Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

Abstract : Structurally precise copper hydrides [CuH{SP(OPr)}(C≡CR)], R = Ph (), CHF (), and CHOMe (), were first synthesized from the polyhydrido copper cluster [CuH{SP(OPr)}] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CHCN)](PF), [NH][SP(OPr)], NaBH, and alkynes along with NEt in THF. , , and 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 Cu cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster co-crystallized with a [Cu(H){SP(OPr)}] () cluster. Six dithiophosphate and three alkynyl ligands stabilize the CuH core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by H NMR spectroscopy for their deuteride derivatives [Cu(D){SP(OPr)}(C≡CR)]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.
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Submitted on : Thursday, March 26, 2020 - 10:47:02 AM
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Rhone P Brocha Silalahi, Guan-Rong Huang, Jian-Hong Liao, Tzu-Hao Chiu, Kiran Kumarvarma Chakrahari, et al.. Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry. Inorganic Chemistry, American Chemical Society, 2020, 59 (4), pp.2536-2547. ⟨10.1021/acs.inorgchem.9b03501⟩. ⟨hal-02472166⟩

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