Reactions of sulfur nitride (S4N4) with antimony pentachloride, antimony pentafluoride, arsenic pentafluoride, phosphorus pentafluoride, and fluorosulfuric acid. Preparation and crystal structures of salts of the S4N42+ cation: (S4N4)(Sb3F14)(SbF6), (S4N4)(SO3F)2, (S4N4)(AsF6)2.cntdot.SO2, (S4N4)(AlCl4)2, and (S4N4)(SbCl6)2

Gillespie, R. J.; Kent, James P.; Sawyer, J. F.; Slim, David R.; Tyrer, J. David

doi:10.1021/ic50225a042

Cited by 46 publications

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“…The previously reported reaction of S 4 N 4 and S 2 O 6 F 2 , according to leads quantitatively to an ionic material, with the presence of the square-planar cation [S 4 N 4 ] 2+ subsequently confirmed by a single-crystal X-ray diffraction study . On the other hand, the radical (CF 3 ) 2 NO achieves tetrasubstitution and binds to all four sulfur atoms in S 4 N 4 [ON(CF 3 ) 2 ] 4 …”

Section: Resultsmentioning

confidence: 67%

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Acyclic Sulfur−Nitrogen Compounds. Syntheses and Crystal and Molecular Structures of Bis((trifluoromethyl)sulfonyl)amine ((CF₃SO₂)₂NH), Magnesium Hexaaquo Bis((trifluoromethyl)sulfonyl)amide Dihydrate ([Mg(H₂O)₆][(CF₃SO₂)₂N]₂·2H₂O), and Bis(bis(fluorosulfonyl)amino)sulfur ((FSO₂)₂NSN(SO₂F)₂)

et al. 1996

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The syntheses of three acyclic (fluorosulfonyl)− or ((trifluoromethyl)sulfonyl)−nitrogen derivatives and their crystal and molecular structures are reported. The structures of bis((trifluoromethyl)sulfonyl)amine (1; (CF3SO2)2NH) and the corresponding anion in magnesium hexaaquo bis((trifluoromethyl)sulfonyl)amide dihydrate (2; [Mg(H2O)6][(CF3SO2)2N]2·2H2O) shed some light on the observed high gas-phase acidity of (CF3SO2)2NH. Extensive electron delocalization in the anion [(CF3SO)2N]- from planar, sp2-hybridized nitrogen into 3d orbitals of sulfur results in a noticeable shortening of the S−N bond on deprotonation. Similar electron delocalization is observed for the third compound, bis(bis(fluorosulfonyl)amino)sulfur (3; (FSO2)2NSN(SO2F)2), which features planar nitrogens with nearly six equidistant S−N bonds and extremely short S−O and S−F bonds. Compounds 2 and 3 have not been reported previously. Their unexpected, accidental formation and their characterization will be discussed. Compound 1 crystallizes in the space group Pccn (No. 56) with a = 16.404(3) Å, b = 5.535(1) Å, c = 9.557(2) Å, and Z = 4. Compound 2 crystallizes in the space group P21/n (No. 14) with a = 6.400(1) Å, b = 14.300(1) Å, c = 14.421(1) Å, β = 97.45(1)°, and Z = 2. Compound 3 crystallizes in the space group P21/c (No. 14) with a = 12.762(1) Å, b = 6.744(1) Å, c = 13.627(1) Å, β = 91.42(1)°, and Z = 4.

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Section: Resultsmentioning

confidence: 67%

“…Again, extensive electron delocalization is observed. The skeleton invites a structural comparison to cyclic SN compounds , with alternating sulfur and nitrogen atoms such as [S 4 N 4 ] 2+ …”

Section: Introductionmentioning

confidence: 99%

Acyclic Sulfur−Nitrogen Compounds. Syntheses and Crystal and Molecular Structures of Bis((trifluoromethyl)sulfonyl)amine ((CF₃SO₂)₂NH), Magnesium Hexaaquo Bis((trifluoromethyl)sulfonyl)amide Dihydrate ([Mg(H₂O)₆][(CF₃SO₂)₂N]₂·2H₂O), and Bis(bis(fluorosulfonyl)amino)sulfur ((FSO₂)₂NSN(SO₂F)₂)

et al. 1996

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“…It is a planar species like the corresponding dication [S4N4] 2+ [60], but the monocation radical has D2h symmetry due to Jahn-Teller distortion. The S3-N1…”

Section: [S4n4] +•mentioning

confidence: 99%

“…dev.) N-S bond distances of 1.550(7) Å and angles: NSN = 118.5(7)°, SNS = 151(2)° [60]. Although a comparison of X-ray and computed bond lengths is not straightforward, the changes in the radical cation geometry seem to be fully consistent with population of the π* SOMO (Figure 12a), which is antibonding for S1-N1, but essentially non-bonding for S3-N1.…”

Section: +mentioning

confidence: 99%

Structures and EPR spectra of binary sulfur–nitrogen radicals from DFT calculations

Boeré

Tuononen

Chivers

et al. 2007

Journal of Organometallic Chemistry

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The scattered electron paramagnetic resonance (EPR) spectroscopic data for binary sulfurnitrogen (S,N) radicals has been compiled and critically assessed. Many of these are inorganic rings or cages. For each species, possible equilibrium structures in the gas phase and the EPR hyperfine coupling (hfc) constants have been calculated with DFT using the B3LYP functional and basis sets of triple- (or better) quality. Good agreement is obtained (through isotopic enrichment). These values were essential for the correct identification of the EPR spectra of this important radical which previously was missassigned to other species.Our results suggest that 33 S data will be equally important for the correct identification of the EPR spectra of other binary S,N species, many of which are cyclic systems, e.g.

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“…Our subsequent SCGVB calculations for the valence π ‐space of the planar S 4 N 4 2+ ring were carried out for the geometry and orientation shown in Figure and again using the standard cc‐pVQZ basis set. The SN nuclear separation, the bond angles, and the molecular point group ( D 4 h ) were based on the crystallographic studies of Gillespie et al, but, as in the case of S 2 N 2 , we do not expect any of our key findings to be sensitive to small changes to this geometry. Our single‐configuration SCGVB wave function for the valence π space of S 4 N 4 2+ is based on a single product of 10 singly occupied nonorthogonal active orbitals π μ that are expanded in the full basis set and it can be written in the following form:

Ψ_{SCGVB} = scriptA ([], ((), \prod_{i = 1}^{40} ϕ_{i} α ϕ_{i} β) ((), \prod_{μ = 1}^{10} π_{μ}) Θ_{0}^{10}),

in which the active‐space total spin function

Θ_{0}^{10}

is expanded in the full spin space, consisting of 42 linearly independent modes of coupling together the spins of 10 electrons so as to achieve an overall singlet state.…”

Section: Theoretical and Computational Detailsmentioning

confidence: 88%

Is the S₂N₂ring a singlet diradical? Critical analysis of alternative valence bond descriptions

Penotti

Karadakov

2018

Int J of Quantum Chemistry

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Rival valence bond (VB) descriptions are investigated for the π-electron systems of the sulfurnitrogen rings S 2 N 2 and S 4 N 4 2+ near equilibrium geometry. The lowest-energy compact spincoupled generalized VB (SCGVB) descriptions are provided by variational optimization of two configurations that are found to be symmetry related to one another. Optimization instead of symmetry-pure single-configuration SCGVB wave functions introduces three-center SNS or NSN orbitals, which seem to be an unnecessary complication. For neither system is much achieved by mixing competing solutions. Breathing orbital VB (BOVB) calculations for S 2 N 2 confirm NN singlet diradical character to be more important than SS singlet diradical character, but the largest contribution (ca. 60%) comes from the symmetry-determined linear combination of four symmetry-equivalent structures that lack any obvious diradical character. Much the same pattern was consistently found using a simple but robust projection of various SCGVB descriptions for S 2 N 2 onto the basis of BOVB structures (plus an orthogonal complement). K E Y W O R D Sbreathing orbital valence bond, π-electron rings, generalized multiconfiguration spin-coupled, S 2 N 2 and S 4 N 4 2+, spin-coupled generalized valence bond (SCGVB) | INTRODUCTIONAlthough various larger (SN) x systems continue to attract considerable experimental and theoretical attention for a wide range of reasons, we should admit from the outset that our own particular interest in the planar S 2 N 2 ring is associated with the somewhat unusual levels of attention that this small molecule has been receiving from theoretical chemists, particularly those specializing in valence bond (VB) theory. A spin-coupled generalized VB (SCGVB, vide infra) description of S 2 N 2 , reported by Gerratt et al., [1] was interpreted at the time as being dominated by SS singlet diradical character but some other studies, [2][3][4][5][6] and especially the very careful breathing orbital VB (BOVB) work of Braïda et al., [2] have seriously questioned the validity of that interpretation. Indeed, Braïda et al. [2] were able to show by partly qualitative arguments that the SCGVB wave function, when stripped to some extent of the delocalization tails on the fully optimized active orbitals, did in fact appear to be consistent with the BOVB viewpoint, in which a structure with NN singlet diradical character was the largest single contributor. We reexamine this issue in the present work, by means of a novel approach utilizing a robust projection of the SCGVB wave function onto the basis of the BOVB structures.While confirming the main gist of the conclusions of Braïda et al., [2] namely that Gerratt et al. [1] may have misinterpreted the results of their SCGVB calculations, we also show that the interpretation of the BOVB description could be interestingly more nuanced than had been supposed.Additionally, as was shown by Thorsteinsson et al., [7] there can exist rival SCGVB-like solutions that are fairly close in energy to the one described by...

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Cited by 46 publications

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Structures and EPR spectra of binary sulfur–nitrogen radicals from DFT calculations

Is the S₂N₂ring a singlet diradical? Critical analysis of alternative valence bond descriptions

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Cited by 46 publications

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Acyclic Sulfur−Nitrogen Compounds. Syntheses and Crystal and Molecular Structures of Bis((trifluoromethyl)sulfonyl)amine ((CF3SO2)2NH), Magnesium Hexaaquo Bis((trifluoromethyl)sulfonyl)amide Dihydrate ([Mg(H2O)6][(CF3SO2)2N]2·2H2O), and Bis(bis(fluorosulfonyl)amino)sulfur ((FSO2)2NSN(SO2F)2)

Acyclic Sulfur−Nitrogen Compounds. Syntheses and Crystal and Molecular Structures of Bis((trifluoromethyl)sulfonyl)amine ((CF3SO2)2NH), Magnesium Hexaaquo Bis((trifluoromethyl)sulfonyl)amide Dihydrate ([Mg(H2O)6][(CF3SO2)2N]2·2H2O), and Bis(bis(fluorosulfonyl)amino)sulfur ((FSO2)2NSN(SO2F)2)

Structures and EPR spectra of binary sulfur–nitrogen radicals from DFT calculations

Is the S2N2ring a singlet diradical? Critical analysis of alternative valence bond descriptions

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Is the S₂N₂ring a singlet diradical? Critical analysis of alternative valence bond descriptions