Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride
Abstract
Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF)x][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF)x][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th–Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th–NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]-vs. comparable thorium imido and oxo complexes.
- Authors:
-
[2];
[2];
[1]
- Department of Chemistry and Biochemistry, University of California, Santa Barbara, USA
- Department of Chemistry, University at Buffalo, State University of New York, Buffalo, USA
- Publication Date:
- Research Org.:
- State Univ. of New York (SUNY), Albany, NY (United States); Univ. of California, Santa Barbara, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1526076
- Alternate Identifier(s):
- OSTI ID: 1610532
- Grant/Contract Number:
- SC-0001861; SC0001136; SC0001861
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 26; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Staun, Selena L., Sergentu, Dumitru-Claudiu, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W. Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9SC01960J.
Staun, Selena L., Sergentu, Dumitru-Claudiu, Wu, Guang, Autschbach, Jochen, & Hayton, Trevor W. Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride. United Kingdom. doi:https://doi.org/10.1039/C9SC01960J
Staun, Selena L., Sergentu, Dumitru-Claudiu, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W. Wed .
"Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride". United Kingdom. doi:https://doi.org/10.1039/C9SC01960J.
@article{osti_1526076,
title = {Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride},
author = {Staun, Selena L. and Sergentu, Dumitru-Claudiu and Wu, Guang and Autschbach, Jochen and Hayton, Trevor W.},
abstractNote = {Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF)x][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF)x][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th–Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th–NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]-vs. comparable thorium imido and oxo complexes.},
doi = {10.1039/C9SC01960J},
journal = {Chemical Science},
number = 26,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {7}
}
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DOI: https://doi.org/10.1039/C9SC01960J
DOI: https://doi.org/10.1039/C9SC01960J
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