Probing the Electronic Structure of a Thorium Nitride Complex by Solid-State 15N NMR Spectroscopy
The solid-state 15N NMR powder spectra of the thorium nitride complex, [K(18-crown-6)(THF)2][(R2N)3Th(μ-15N)Th(NR2)3] ([K][1-15N], R = SiMe3), and the thorium amide complex, [Th(NR2)3(15NH2)] (2-15N), were recorded. The spectrum for [K][1-15N] represents the first reported solid-state 15N NMR data for an actinide complex. The experimentally measured tensor spans are Ω = 847 ppm for [K][1-15N] and Ω = 237 ppm for 2-15N. Both shielding tensors exhibit axial symmetry, which for [K][1-15N] is consistent with a local rotational symmetry of its 15N-labeled nitride ligand. For 2-15N, the axial asymmetry can be rationalized by a quasi-free Th-NH2 bond rotation in the solid-state. Density functional theory calculations overestimate the tensor span somewhat for [K][1-15N], but provide isotropic shifts in good agreement with both the solid-state and solution values for both complexes. Natural localized molecular orbital analyses of the nuclear shielding reveal that the larger tensor span in [K][1-15N] vs 2-15N is primarily a consequence of more pronounced covalency of the σ(N-Th) bonds and large spin-orbit coupling due to significant Th 5f orbital contribution to those bonds, impacting the principal components of the shielding tensor perpendicular to the Th-N-Th axis. Overall, our analysis confirms the involvement of the 5f orbitals in Th-N multiple bonds and further demonstrates the value of solid-state NMR spectroscopy for interrogating actinide-ligand bonding.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
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| Enthalten in: |
Inorganic chemistry - 59(2020), 14 vom: 20. Juli, Seite 10138-10145 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Sergentu, Dumitru-Claudiu [VerfasserIn] |
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| Anmerkungen: |
Date Revised 20.07.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.0c01263 |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM311728707 |
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| 500 | |a Date Revised 20.07.2020 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The solid-state 15N NMR powder spectra of the thorium nitride complex, [K(18-crown-6)(THF)2][(R2N)3Th(μ-15N)Th(NR2)3] ([K][1-15N], R = SiMe3), and the thorium amide complex, [Th(NR2)3(15NH2)] (2-15N), were recorded. The spectrum for [K][1-15N] represents the first reported solid-state 15N NMR data for an actinide complex. The experimentally measured tensor spans are Ω = 847 ppm for [K][1-15N] and Ω = 237 ppm for 2-15N. Both shielding tensors exhibit axial symmetry, which for [K][1-15N] is consistent with a local rotational symmetry of its 15N-labeled nitride ligand. For 2-15N, the axial asymmetry can be rationalized by a quasi-free Th-NH2 bond rotation in the solid-state. Density functional theory calculations overestimate the tensor span somewhat for [K][1-15N], but provide isotropic shifts in good agreement with both the solid-state and solution values for both complexes. Natural localized molecular orbital analyses of the nuclear shielding reveal that the larger tensor span in [K][1-15N] vs 2-15N is primarily a consequence of more pronounced covalency of the σ(N-Th) bonds and large spin-orbit coupling due to significant Th 5f orbital contribution to those bonds, impacting the principal components of the shielding tensor perpendicular to the Th-N-Th axis. Overall, our analysis confirms the involvement of the 5f orbitals in Th-N multiple bonds and further demonstrates the value of solid-state NMR spectroscopy for interrogating actinide-ligand bonding | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Kent, Greggory T |e verfasserin |4 aut | |
| 700 | 1 | |a Staun, Selena L |e verfasserin |4 aut | |
| 700 | 1 | |a Yu, Xiaojuan |e verfasserin |4 aut | |
| 700 | 1 | |a Cho, Herman |e verfasserin |4 aut | |
| 700 | 1 | |a Autschbach, Jochen |e verfasserin |4 aut | |
| 700 | 1 | |a Hayton, Trevor W |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:59 |g year:2020 |g number:14 |g day:20 |g month:07 |g pages:10138-10145 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.0c01263 |3 Volltext |
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