Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry
Abstract
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 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(C≡CR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.
- Authors:
-
[2];
[3];
[4];
[1]
- National Dong Hwa Univ. (Taiwan)
- SRM Inst. of Science and Technology, Kattankulathur (India)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1631228
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 4; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrocarbons; Anions; Copper; Ligands; Metal clusters
Citation Formats
Brocha Silalahi, Rhone P., Huang, Guan-Rong, Liao, Jian-Hong, Chiu, Tzu-Hao, Chakrahari, Kiran Kumarvarma, Wang, Xiaoping, Cartron, Julien, Kahlal, Samia, Saillard, Jean-Yves, and Liu, C. W. Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.9b03501.
Brocha Silalahi, Rhone P., Huang, Guan-Rong, Liao, Jian-Hong, Chiu, Tzu-Hao, Chakrahari, Kiran Kumarvarma, Wang, Xiaoping, Cartron, Julien, Kahlal, Samia, Saillard, Jean-Yves, & Liu, C. W. Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry. United States. https://doi.org/10.1021/acs.inorgchem.9b03501
Brocha Silalahi, Rhone P., Huang, Guan-Rong, Liao, Jian-Hong, Chiu, Tzu-Hao, Chakrahari, Kiran Kumarvarma, Wang, Xiaoping, Cartron, Julien, Kahlal, Samia, Saillard, Jean-Yves, and Liu, C. W. Fri .
"Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry". United States. https://doi.org/10.1021/acs.inorgchem.9b03501. https://www.osti.gov/servlets/purl/1631228.
@article{osti_1631228,
title = {Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry},
author = {Brocha Silalahi, Rhone P. and Huang, Guan-Rong and Liao, Jian-Hong and Chiu, Tzu-Hao and Chakrahari, Kiran Kumarvarma and Wang, Xiaoping and Cartron, Julien and Kahlal, Samia and Saillard, Jean-Yves and Liu, C. W.},
abstractNote = {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 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(C≡CR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.},
doi = {10.1021/acs.inorgchem.9b03501},
journal = {Inorganic Chemistry},
number = 4,
volume = 59,
place = {United States},
year = {Fri Jan 24 00:00:00 EST 2020},
month = {Fri Jan 24 00:00:00 EST 2020}
}
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