Abstract
Structurally precise copper hydrides [Cu11H2{S2P(OiPr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(OiPr)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(OiPr)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(OiPr)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(OiPr)2}6(CCR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.
Original language | English |
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Pages (from-to) | 2536-2547 |
Number of pages | 12 |
Journal | Inorganic Chemistry |
Volume | 59 |
Issue number | 4 |
DOIs | |
State | Published - Feb 17 2020 |
Funding
This work was supported by the Ministry of Science and Technology of Taiwan (MOST 106-2113-M-259-010, 108-2923-M-259-001) the France–Taiwan ANR-MOST 2018 program (project Nanoalloys) and the GENCI French National Computer Resource Center (A0030807367). We thank Radu Custelcean and Andrey Kovalevsky for their help provided with the sample screening and data collection for 2[1][4]·acetone using the single crystal X-ray diffractometers located in the Chemical Science Division and the SNS Protein Crystallography Lab at ORNL. Single-crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC. This work was supported by the Ministry of Science and Technology of Taiwan (MOST 106-2113-M-259-010, 108-2923-M-259-001), the France–Taiwan ANR-MOST 2018 program (project Nanoalloys), and the GENCI French National Computer Resource Center (A0030807367). We thank Radu Custelcean and Andrey Kovalevsky for their help provided with the sample screening and data collection for 2[1][4]·acetone using the single crystal X-ray diffractometers located in the Chemical Science Division and the SNS Protein Crystallography Lab at ORNL. Single-crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC.