Covalent Bonds in α‐SnF2 Monitored by J‐Couplings in Solid‐State NMR Spectra

Bräuniger, Thomas; Ghedia, Stefan; Jansen, Martin

doi:10.1002/zaac.201000176

Cited by 15 publications

(4 citation statements)

References 29 publications

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“…The much larger Ω measured for the cation in 6 dwarfs those for all of the triflate complexes, again demonstrating that there are fundamental differences between the seemingly analogous chloride and triflate complexes. In this regard, it is well-known from 119 Sn SSNMR studies of Sn(II) complexes − and 207 Pb SSNMR studies of Pb(II) complexes, − that as the p-orbital character of the HOMO metal centered “lone pair” increases, Ω is usually observed to increase as well. Among the triflate complexes, 3 – 5 have the most positive values of δ iso , larger values of Ω, and possess the least spherically symmetric Sn coordination environments.…”

Section: Resultsmentioning

confidence: 98%

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

et al. 2012

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A series of tin(II) triflate and chloride salts in which the cations are complexed by either cyclic or acyclic polyether ligands and which have well-characterized single-crystal X-ray structures are investigated using a variety of experimental and computational techniques. Mössbauer spectroscopy illustrates that the triflate salts tend to have valence electrons with higher s-character, and solid-state NMR spectroscopy reveals marked differences between superficially similar triflate and chloride salts. Cyclic voltammetry investigations of the triflate salts corroborate the results of the Mössbauer and NMR spectroscopy and reveal substantial steric and electronic effects for the different polyether ligands. MP2 and DFT calculations provide insight into the effects of ligands and substituents on the stability and reactivity of the low-valent metal atom. Overall, the investigations reveal the existence of more substantial binding between tin and chlorine in comparison to the triflate substituent and provide a rationale for the considerably increased reactivity of the chloride salts.

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Section: Resultsmentioning

confidence: 98%

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

et al. 2012

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“…The first of these peaks has a δ iso value close to that of BaF 2 (−14.2 ppm), where fluoride ions occupy Ba 4 -coordinated tetrahedral sites. The second peak aligns with the average δ iso value of α-SnF 2 (−46 ppm), in which fluorine is triply coordinated with short Sn–F distances . Based on these comparisons, we assign these features at −14 and −45 ppm to broadly Ba-rich and Sn-rich fluorine environments, respectively.…”

Section: Resultsmentioning

confidence: 61%

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Mercadier,

Coles,

Duttine

et al. 2023

J. Am. Chem. Soc.

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Introducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F2 fluorites have previously been proposed to exhibit two forms of disorder within their cationic host frameworks: occupational disorder from randomly distributed M and Sn cations and orientational disorder from Sn(II) stereoactive lone pairs. Here, we characterize the structure and fluoride-ion dynamics of cubic BaSnF4, using a combination of experimental and computational techniques. Rietveld refinement of the X-ray diffraction (XRD) data confirms an average fluorite structure with {Ba,Sn} cation disorder, and the 119Sn Mössbauer spectrum demonstrates the presence of stereoactive Sn(II) lone pairs. X-ray total-scattering PDF analysis and ab initio molecular dynamics simulations reveal a complex local structure with a high degree of intrinsic fluoride-ion disorder, where 1/3 of fluoride ions occupy octahedral “interstitial” sites: this fluoride-ion disorder is a consequence of repulsion between Sn lone pairs and fluoride ions that destabilizes Sn-coordinated tetrahedral fluoride-ion sites. Variable-temperature 19F NMR experiments and analysis of our molecular dynamics simulations reveal highly inhomogeneous fluoride-ion dynamics, with fluoride ions in Sn-rich local environments significantly more mobile than those in Ba-rich environments. Our simulations also reveal dynamical reorientation of the Sn lone pairs that is biased by the local cation configuration and coupled to the local fluoride-ion dynamics. We end by discussing the effect of host-framework disorder on long-range diffusion pathways in cubic BaSnF4.

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“…By comparing spectra at different spinning speeds (Figure S4), the isotropic resonance of the Sn II species can be determined to be at δ ≈ −730 ppm. We also note that the strong resonance line in Figure 6 exhibits symmetrical low shoulders, which are typical for Sn spectra affected by indirect couplings [57–59] . In Sn 3 P 8 N 16 , the predominant coupling partners are 14 N (99.6 % natural abundance) via one bond and 31 P (100 % n.…”

Section: Resultsmentioning

confidence: 72%

“…We also note that the strong resonance line in Figure 6 exhibits symmetrical low shoulders, which are typical for Sn spectra affected by indirect couplings. [57][58][59] In Sn 3 P 8 N 16 , the predominant coupling partners are 14 N (99.6 % natural abundance) via one bond and 31 P (100 % n. a.)…”

Section: Solid-state Magic-angle Spinning (Mas) Nuclear Magnetic Reso...mentioning

confidence: 99%

Mixed Tin Valence in the Tin(II/IV)‐Nitridophosphate Sn₃P₈N₁₆

Ambach,

Koldemir,

Witthaut

et al. 2024

Chemistry A European J

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Sn3P8N16 combines the structural versatility of nitridophosphates and Sn within one compound. It was synthesized as dark gray powder in a high‐pressure high‐temperature reaction at 800 °C and 6 GPa from Sn3N4 and P3N5. The crystal structure was elucidated from single‐crystal diffraction data (space group C2/m (no. 12), a = 12.9664(4), b = 10.7886(4), c = 4.8238(2) Å, β = 109.624(1)°) and shows a 3D‐network of PN4 tetrahedra, incorporating Sn in oxidation states +II and +IV. The Sn cations are located within eight‐membered rings of vertex‐sharing PN4 tetrahedra, stacked along the [001] direction. A combination of solid‐state nuclear magnetic resonance spectroscopy, 119Sn Mössbauer spectroscopy and density functional theory calculations was used to confirm the mixed oxidation of Sn. Temperature‐dependent powder X‐ray diffraction measurements reveal a low thermal expansion of 3.6 ppm/K up to 750 °C, beyond which Sn3P8N16 starts to decompose.

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Covalent Bonds in α‐SnF₂ Monitored by J‐Couplings in Solid‐State NMR Spectra

Cited by 15 publications

References 29 publications

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Mixed Tin Valence in the Tin(II/IV)‐Nitridophosphate Sn₃P₈N₁₆

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Covalent Bonds in α‐SnF2 Monitored by J‐Couplings in Solid‐State NMR Spectra

Cited by 15 publications

References 29 publications

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF4

Mixed Tin Valence in the Tin(II/IV)‐Nitridophosphate Sn3P8N16

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Covalent Bonds in α‐SnF₂ Monitored by J‐Couplings in Solid‐State NMR Spectra

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Mixed Tin Valence in the Tin(II/IV)‐Nitridophosphate Sn₃P₈N₁₆