Generation of C<sub>6</sub>S<sub>6</sub> and its radical anion and cation in the gas phase

Sülzle, Detlev; Beye, N.; Fanghänel, E.; Schwarz, Helmut

doi:10.1002/cber.19891221233

Cited by 30 publications

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References 14 publications

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“…Moreover, the triplet states of C 3 S 3 ( D 3 h ) and C 4 S 4 ( D 4 h ) are local minimum while the C 5 S 5 ( D 5 h ) triplet is a second-order saddle point (NIMAG = 2). D 2 h C 6 S 6 , 15b, the most stable hexathiocarbon, and its D 3 h , D 3 d , and C 2 isomers are minima. The C 6 S 6 isomer energy order is in agreement with literature reports 15 (Table ); the D 2 h structure is lowest in energy, followed by D 3 h (relative energy 7.7 kcal/mol), D 3 d (37.4 kcal/mol), and C 2 (41.1 kcal/mol).…”

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“…As for C 6 S 6 , , the stability of C 6 S 6 2- is determined by the balance between aromatic stabilization, ring strain, and C−S and S−S bond strength affects. The most stable cyclic C 6 S 6 2- isomer, like C 6 S 6 , has D 2 h symmetry and a strongly delocalized hexagonal carbon ring with C−C bond lengths of approximately the benzene value, 1.40 Å.…”

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confidence: 99%

“…D 2h C 6 S 6 , 15b,16 the most stable hexathiocarbon, and its D 3h , D 3d , and C 2 isomers are minima. The C 6 S 6 isomer energy order is in agreement with literature reports 15 (Table3); the D 2h structure is lowest in energy, followed by D 3h (relative energy 7.7 kcal/mol), D 3d (37.4 kcal/mol), and C 2 (41.1 kcal/mol).The most stable C 6 S 6 isomer is not monocyclic but has C 2v symmetry and two fused five-membered rings (Figure…”

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A Theoretical and Structural Investigation of Thiocarbon Anions

et al. 2003

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Density functional theory energies, geometries, and population analyses as well as nucleus-independent chemical shifts (NICS) have been used to investigate the structural and magnetic evidence for cyclic CnSn(2-) and CnSn (n = 3-6) electron delocalization. Localized molecular orbital contributions to NICS, computed by the individual gauge for localized orbitals method, dissect pi effects from the sigma single bonds and lone pair influences. CnSn(2-) (n = 3-5) structures in Dnh symmetry are minima. Their aromaticity decreases with increasing ring size. C3S3(2-) is both sigma and pi aromatic, while C4S4(2-) and C5S5(2-) are much less aromatic. NICS(0)pi, the C-C(pi) contribution to NICS(0) (i.e., at the ring center), decreases gradually with ring size. In contrast, cyclic C6S6(2-) prefers D2h symmetry due to the balance between aromaticity, strain energy, and the S-S bond energies and is as aromatic as benzene. The theoretical prediction that C6S6(6-) has D6h minima was confirmed by X-ray structure analysis. Comparisons between thiocarbons and oxocarbons based on dissected NICS analysis show that CnSn(2-) (n = 3-5) and C6S6(6-) are less aromatic in Dnh symmetry than their oxocarbon analogues.

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A Theoretical and Structural Investigation of Thiocarbon Anions

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Ab initio MO calculations on 1,2-dithietes and valence isomers

Mann

Fabian

1996

Int. J. Quantum Chem.

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mThe valence isomerization of the 1,2-dithiete parent compound to the open-chain dithial was studied by CASSCF multiconfiguration methods including the CASPT2 perturbational treatment. The isomerization energy remains small at the highest level of theory. In agreement with Jonas and Frenking, the cyclic structure is only then preferred over the acyclic ones if f-functions on the sulfur atoms are considered. If they are included, the 1,2-dithiete is more stable by 3.8 kcal/mol and the barrier amounts to 24.9 kcal/mol at the CASPT2(8,8)/6-31G(2 df)//MP2/6-31G* level of theory. According to MP2/6-31G* geometry optimizations, substitution of H by NH, and CH, reduces the stability of the 1,2-dithiete ring structures relative to the open-chain dithiocarbonyl structures, whereas the inverse holds for acceptor substitution by CN and CF,. A higher stability of benzodithiete relative to orfho-dithiobenzoquinone is predicted at all employed levels of theory. This is in good agreement with conclusions drawn from experimental results. Whereas the experimental microwave geometry of 1,2-dithiete is well reproduced theoretically, the experimental electron diffraction geometry of 3,4-bis-(trifluoromethyl)-1,2-dithiete differs from the calculated one. 0 1996 John Wiley & Sons, Inc.

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