Structures, Energies, and Fundamental Vibrations of the Sulfonium Ions H3Sn+ (n = 1-4)

Otto, André; Steudel, Ralf

doi:10.1002/1521-3749(200010)626:10<2063::aid-zaac2063>3.0.co;2-0

Cited by 5 publications

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“…By means of Fourier transform ion cyclotron resonance spectroscopy the protonation of the gaseous homocycles S 6 ( D 3 d symmetry) and S 8 ( D 4 d ) has been determined as exothermic by −702 and −783 kJ mol -1 , respectively (Gibbs energies of protonation; ±1 kJ mol -1 ) . Although the structures of the species [HS 6 ] + and [HS 8 ] + produced in these experiments are unknown, the basicity data obtained are comparable to the protonation enthalpy of H 2 S, which has been calculated at the G2 level of theory as −702 kJ mol -1 at 298 K, in excellent agreement with previous calculations 17 and with the experimental value of −705 kJ mol -1 . To the best of our knowledge, protonation experiments of sulfur rings in solution have not been reported.…”

Section: Introductionsupporting

confidence: 87%

“…Because the proton affinities of the neutral sulfur molecules S n are similar in value to those of H 2 S (see Introduction) and H 2 S 2 (718 kJ mol -1 ), it should be possible to prepare solid compounds of composition [HS n ]X ( n = 6−8; X: univalent anion of low basicity) in a fashion similar to that of the crystalline salts [H 3 S][SbF 6 ], [H 3 S 2 ][AsF 6 ], and [H 3 S 2 ][SbF 6 ], which have been prepared from H 2 S and H 2 S 2 , respectively, by protonation in the superacidic mixtures HF/AsF 5 and HF/SbF 5 . Access to the species [HS n ]X with n = 2−5 may be more difficult.…”

Section: Resultsmentioning

confidence: 99%

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Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)

2004

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The structures and thermodynamic properties of 32 cations of composition [HS n ] + with n ) 2-8 have been studied by ab initio methods at the G3X(MP2) level of theory. In the global minimum structures, the proton binds to a single sulfur atom and, except for n ) 2, this also holds for the less stable isomers. The binding energies at 0 K range from 619.4 kJ mol -1 in [HS 2 ] + to 835.6 kJ mol -1 in [S 5 -SH] + , which represents the global minimum structure of composition [HS 6 ] + . The protonated branched rings are also the global minimum structures in the case of S 7 and S 8 , whereas [HS 5 ] + is most stable with a five-membered homocycle. The smaller cations [HS n ] + (n ) 2-4) are all chainlike with the hydrogen atom at a chain end. Unexpectedly, singlet chainlike structures of [HS n ] + (n ) 2-8) with the hydrogen terminating the chain at one end are more stable than the corresponding triplet chains. The protonation of neutral sulfur molecules always takes place at the atom of highest negative charge and the charge transfer to the proton is between 0.77 and 0.86 electrons. The S-H bond lengths are calculated as in the range 135-139 pm. The effect of protonation on the sulfursulfur bonds is dramatic, as can be seen in the strong bond length alternation within the cyclic or chainlike structures with the weakest SS bonds originating from the three-coordinate atoms. Hence, there is a pronounced bond activation by protonation. The calculated gas-phase basicities of S 6 and S 8 are in good accord with the experimental values.

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Section: Introductionsupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)

2004

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“…The hexafluoroantimonate salt of 52 is a stable white solid that reacts with water to produce H 2 S. This reaction can be conveniently used to generate H 2 S. The ion 52 has been thoroughly characterized by vibrational spectroscopy and normal coordinate analysis. 156 Ion 52 is of C 3v symmetry and has a bond angle of 94.2 , which is slightly larger than that of H 2 S (92.1 ). 151,152 In addition, SH 3 þ and its isotopomers (H 3 S þ , HD 2 S þ , D 3 S þ ) were also observed by various spectroscopic methods.…”

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confidence: 90%

Heterocations in Superacid Systems

Oláh¹,

Prakash²,

Molnár³

et al. 2008

Superacid Chemistry

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Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Steudel

Wong

Steudel

2005

Chemistry A European J

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Complex formation between gaseous Li+ ions and sulfur-containing neutral ligands, such as H2S, Me2Sn (n = 1-5; Me = CH3) and various isomers of hexasulfur (S6), has been studied by ab initio MO calculations at the G3X(MP2) level of theory. Generally, the formation of LiS(n) heterocycles and clusters is preferred in these reactions. The binding energies of the cation in the 29 complexes investigated range from -88 kJ mol(-1) for [H2SLi]+ to -189 kJ mol(-1) for the most stable isomer of [Me2S5Li]+ which contains three-coordinate Li+. Of the various S6 ligands (chair, boat, prism, branched ring, and triplet chain structures), two isomeric complexes containing the S5==S ligand have the highest binding energies (-163+/-1 kJ mol(-1)). However, the global minimum structure of [LiS6]+ is of C(3v) symmetry with the six-membered S(6) homocycle in the well-known chair conformation and three Li--S bonds with a length of 256 pm (binding energy: -134 kJ mol(-1)). Relatively unstable isomers of S6 are stabilized by complex formation with Li+. The interaction between the cation and the S6 ligands is mainly attributed to ion-dipole attraction with a little charge transfer, except in cations containing the six sulfur atoms in the form of separated neutral S2, S3, or S4 units, as in [Li(S3)2]+ and [Li(S2)(S4)]+. In the two most stable isomers of the [LiS6]+ complexes, the number of S--S bonds is at maximum and the coordination number of Li+ is either 3 or 4. A topological analysis of all investigated complexes revealed that the Li--S bonds of lengths below 280 pm are characterized by a maximum electron-density path and closed-shell interaction.

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Structures, Energies, and Fundamental Vibrations of the Sulfonium Ions H3Sn+ (n = 1-4)

Abstract: ± wurden mit der G2-Methode berechnet. Fu È r n = 1±3 liegen die Enthalpien im Bereich 639±731 kJ mol ±1 .

Cited by 5 publications

References 11 publications

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)

Heterocations in Superacid Systems

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

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Structures, Energies, and Fundamental Vibrations of the Sulfonium Ions H3Sn+ (n = 1-4)

Abstract: ± wurden mit der G2-Methode berechnet. Fu È r n = 1±3 liegen die Enthalpien im Bereich 639±731 kJ mol ±1 .

Cited by 5 publications

References 11 publications

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules Sn (n = 2−8)

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules Sn (n = 2−8)

Heterocations in Superacid Systems

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

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Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)

Electrophilic Attack on Sulfur−Sulfur Bonds. 1. Protonation of Various Isomers of the Homoatomic Sulfur Molecules S_n (n = 2−8)