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Title: Terminal and bridging fluorine ligands in TiF₄ as studied by ¹⁹F NMR in solids
Authors: Murakami, Miwa  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0001-6209-4450 (unconfirmed)
Noda, Yasuto  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0003-4971-4023 (unconfirmed)
Takegoshi, K.
Author's alias: 村上, 美和
野田, 泰斗
竹腰, 清乃理
Keywords: TiF₄
¹⁹F chemical-shift anisotropy
DFT
Spinning sideband
Rotation-synchronized DANTE
Issue Date: Sep-2019
Publisher: Elsevier B.V.
Journal title: Solid State Nuclear Magnetic Resonance
Volume: 101
Start page: 82
End page: 88
Abstract: To examine bonding nature of fluorine ligands in a metal coordinated system, ¹⁹F high-resolution solid-state NMR has been applied to TiF₄, which bears both bridging and terminal fluorines. Observed 12 isotropic signals are assigned to 12 crystallographically different fluorines (6 terminal and 6 bridging fluorines) in TiF₄ by referring to the calculated isotropic shifts using density functional theory (DFT). The isotropic chemical shift (δiso) for terminal F (FT) appears at high frequency (420–480 ppm from δ(CCl3F) = 0 ppm) with large shielding anisotropy Δσ ∼ 850 ppm. Whereas the δiso and Δσ values for bridging F (FB) are moderate; δiso ∼ 0–25 ppm and Δσ ∼ 250 ppm. The origin of the observed high-frequency shift for FT is ascribed to the second-order paramagnetic shift with increased covalency, shorter Ti–F bonds, and smaller energy difference between the occupied and vacant orbitals. Examination of the orientation of the shielding tensor relative to the molecular structure shows that the most deshielded component of the shielding tensor is oriented along the Ti–F bond. The characteristic orientation is consistent with a Ti–F σ bond formed by dYZ of Ti and pz of F. Further, we show that the selectively observed spinning sideband patterns and the theoretical patterns with the calculated Δσ and η (shielding asymmetry) values are not consistent with each other for FB, indicating deficiency of the present DFT calculation in evaluating Δσ.
Rights: © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/.
The full-text file will be made open to the public on 1 September 2021 in accordance with publisher's 'Terms and Conditions for Self-Archiving'.
この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
This is not the published version. Please cite only the published version.
URI: http://hdl.handle.net/2433/245036
DOI(Published Version): 10.1016/j.ssnmr.2019.05.007
PubMed ID: 31132715
Appears in Collections:Journal Articles

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