Quantum chemical study of thiosulfinic acids and their anions

Mikołajczyk, M.; Cypryk, Marek; Krasiński, Grzegorz

doi:10.1016/j.theochem.2008.05.024

Cited by 6 publications

(6 citation statements)

References 19 publications

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“…trans-HSSOH was found to be energetically slightly more stable by about 4 kJ/ mol than the cis conformer [17]. This has been confirmed by our high-level coupled-cluster calculations (predicted energy difference of 2.0 kJ/mol) as well as by a very recent study of Mikolajczyk et al [18].…”

Section: Introductionsupporting

confidence: 89%

The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Koerber

Baum

Hahn

et al. 2009

Journal of Molecular Spectroscopy

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Section: Introductionsupporting

confidence: 89%

The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Koerber

Baum

Hahn

et al. 2009

Journal of Molecular Spectroscopy

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“…BD(T), CCSD(T), and QCISD(T) predict 11 to be 5.3, 5.3, and 5.1 kcal/mol, respectively, lower in energy than 11a . Similarly, 1 is predicted to undergo condensation with methanesulfenic acid ( 8 ) to give methanesulfinothioic acid ( 12 ) , and hydro(methanethiolato)oxosulfur ( 12a ) (eq , Figure ). BD(T), CCSD(T), and QCISD(T) predict 12 to be 5.3 kcal/mol lower in energy than 12a .…”

Section: Resultsmentioning

confidence: 99%

“…Hydrogen thioperoxide ( 1 ) and sulfenic acids (R–SOH) exist as sulfenyl (H–SOH, 1 ) and sulfinyl (H 2 SO, C s , 1a ) tautomers (eq ). − Although there are a few exceptions, generally the sulfenyl tautomer is more stable than the corresponding sulfinyl tautomer. Analogous to sulfenic acids, hydrogen thioperoxide is expected to have electrophilic and nucleophilic character, to undergo condensation reactions (cyclodehydration, dehydrative cyclocondensation, self-condensation), and to react with 1,3-dicarbonyl compounds. − In this study, the mechanisms of the tautomerization of 1 (eq ), its condensation to form the parent thiosulfinic acid (sulfinothioic acid, 2 ) (eq ), , its condensation with other sulfenic acids to form organosulfur compounds (eq ), its condensation with selenenic acids 4 to form products 5 containing sulfur–selenium bonds (eq ), − and its C-sulfenylation and O-sulfenylation of 2,4-pentanedione (acetylacetone, Figure , eq ) have been investigated in order to enable a fuller understanding of and deeper insight into the chemistry of the sulfenyl and sulfinyl functional groups in 1 and in sulfenic acids. There are only a few procedures for preparing a diverse range of products with S–Se bonds, and compounds containing S–Se bonds have been implicated in biological processes. − The mechanisms of C-sulfenylation and O-sulfenylation of 1,3-dicarbonyl compounds are also of importance in the detection of protein sulfenic acids (protein–SOH). − …”

Section: Introductionmentioning

confidence: 99%

Mechanisms of Reactions of Sulfur Hydride Hydroxide: Tautomerism, Condensations, and C-Sulfenylation and O-Sulfenylation of 2,4-Pentanedione

Freeman

2015

J. Phys. Chem. A

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The conformations, equilibrium structures, hydrogen bonds, and non-covalent interactions involved in the mechanisms of tautomerization, condensations, and C-sulfenylation and O-sulfenylation of 2,4-pentanedione by sulfur hydride hydroxide (hydrogen thioperoxide, oxadisulfane, H-SOH) have been studied using BD(T), CCSD(T), and QCISD(T) with the cc-pVTZ basis set and using B3LYP, B3PW91, CAM-B3LYP, PBE1PBE, PBEh1PBE, LC-ωPBE, M06-2X, and ωB97XD with the 6-311+G(d,p) basis set. All levels of theory predict the sulfenyl (H-SOH) tautomer of hydrogen thioperoxide to be lower in energy than the sulfinyl (H2S═O) tautomer. Four reasonable mechanisms were considered for the tautomerization of the sulfenyl tautomer of hydrogen thioperoxide to the sulfinyl tautomer: a cyclic three-membered water-free transition state (TS, CCSD(T) activation energy barrier E(⧧) = 65.1 kcal/mol), a cyclic five-membered transition state with one water molecule (TSH2O, E(⧧) = 31.1 kcal/mol), a cyclic seven-membered transition state with two water molecules (TS2H2O, E(⧧) = 14.5 kcal/mol), and a cyclic nine-membered transition state with three water molecules (TS3H2O, E(⧧) = 5.6 kcal/mol). The mechanisms involve hydrogen-bonded reactant complexes and hydrogen-bonded product complexes. The CCSD(T)-predicted energy barriers for the condensation of hydrogen thioperoxide to form thiosulfinic acid through transition states with zero, one, and two waters are E(⧧) = 42.0, 18.3, and 0 kcal/mol, respectively. Mixed condensation reactions are predicted to afford organosulfur products and compounds containing sulfur-selenium bonds. Hydrogen thioperoxide is predicted to add to 2,4-pentanedione to form C-sulfenylated (sulfide, thioether) and O-sulfenylated (sulfenate ester) products. Similar mechanistic trends and reaction pathways are observed in the tautomerism, condensations, and C-sulfenylation and O-sulfenylation reactions of hydrogen thioperoxide. The water molecules set up proton relay networks (bridges) that reduce ring strain, generate favorable conformations for reactivity, lower energy barriers, and increase the numbers of stabilizing hydrogen bonds and nonbonding interactions.

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“…The first computational studies on sulfinothioic acid ( 2 ) using HF , were followed by studies using MP2, ,, and B3LYP . Owing to a large number of allotropes sulfur has unusually large variations in its bonding properties.…”

Section: Resultsmentioning

confidence: 99%

“…It is seen in TS1 that the atomic charge on the sulfur atom (S1) that is becoming the sulfinyl sulfur in the product (2) has significantly increased positive charge relative to ground state (1) whereas the sulfur atom (S2) that is becoming the sulfenyl sulfur in the product (2) has decreased positive charge relative to (1) ( The first computational studies on sulfinothioic acid (2) using HF 52,53 were followed by studies using MP2, 20,54,55 and B3LYP. 56 Owing to a large number of allotropes sulfur has unusually large variations in its bonding properties. Sulfur− sulfur single bonds are extraordinary flexible and have bond lengths that vary from 1.7 to 3.0 Å and bond angles between 90 and 180°.…”

Section: Supporting Information)mentioning

confidence: 99%

Dehydrative Cyclocondensation Mechanisms of Hydrogen Thioperoxide and of Alkanesulfenic Acids

et al. 2012

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Structural features of hydrogen thioperoxide (oxadisulfane, H–S–O–H) and of alkanesulfenic acids (R–S–O–H; R = CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, C(CH3)3, CF3, CCl3) and the mechanisms of their dehydrative cyclocondensation to the respective sulfinothioic acid (H–(SO)–S–H) and alkyl alkanethiosulfinates (R–(SO)–S–R) have been studied using coupled cluster theory with single and double and perturbative triple excitations [CCSD(T)] and quadratic configuration interaction with single and double and perturbative triple excitations [QCISD(T)] with the cc-pVDZ basis set and also using second-order Møller-Plesset perturbation theory (MP2) and the hybrid density functionals B3LYP, B3PW91, and PBE1PBE with the 6-311+G(d,p) basis set. The concerted cyclodehydration mechanisms include cyclic five-center transition states with relatively long distance sulfur–sulfur bonding interactions. Attractive and repulsive nonbonding interactions are predicted in the sulfenic acids, transition states, and thiosulfinates. In the alkyl alkanethiosulfinates attractive cyclic C–H----OS nonbonding interactions are predicted. CCSD(T) and QCISD(T) predict similar values for the relative energies and CCSD(T) predicts the barrier to the cyclocondensation of H–S–O–H to sulfinothioic acid (H–(SO)–S–H) to be 41.8 kcal/mol, and barriers in the range of 37.5 to 39.6 kcal/mol are predicted for the condensation of alkanesulfenic acids to alkyl alkanethiosulfinates.

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Quantum chemical study of thiosulfinic acids and their anions

Cited by 6 publications

References 19 publications

The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Mechanisms of Reactions of Sulfur Hydride Hydroxide: Tautomerism, Condensations, and C-Sulfenylation and O-Sulfenylation of 2,4-Pentanedione

Dehydrative Cyclocondensation Mechanisms of Hydrogen Thioperoxide and of Alkanesulfenic Acids

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