Heats of formation and bond dissociation energies of some simple sulfur- and halogen-containing molecules

Takacs, G. A.

doi:10.1021/je60077a020

Cited by 32 publications

(23 citation statements)

References 11 publications

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“…For example, the S-S BDE of ClS-SCl is 78.8 kcal/mol reported by Claydon through heats of formation measured by calorimeters, [14] but 46 ± 7 kcal/mol measured with equivalent method in Takacs' study. [15] Similar observations have also been noted for the S-S BDE of Ph-S-S-Ph reported by Bausch [16] and Hoff et al [17] (55 ± 2 kcal/mol with electrochemistry method and 43 kcal/mol based on the enthalpy of hydrogenation with scanning calorimetry). Alternatively, theoretical methods have also been used to evaluate the S-S BDEs of disulfides.…”

Section: Introductionsupporting

confidence: 86%

“…Furthermore, the different experimental methods in these studies may give distinct BDEs. For example, the S―S BDE of ClS–SCl is 78.8 kcal/mol reported by Claydon through heats of formation measured by calorimeters, but 46 ± 7 kcal/mol measured with equivalent method in Takacs' study . Similar observations have also been noted for the S―S BDE of Ph–S–S–Ph reported by Bausch and Hoff et al (55 ± 2 kcal/mol with electrochemistry method and 43 kcal/mol based on the enthalpy of hydrogenation with scanning calorimetry).…”

Section: Introductionsupporting

confidence: 81%

“…To the best of our knowledge, less than 30 experimental S-S BDE values of disulfides have been reported. [12][13][14][15][16][17][18][19][20] Furthermore, the different experimental methods in these studies may give distinct BDEs. For example, the S-S BDE of ClS-SCl is 78.8 kcal/mol reported by Claydon through heats of formation measured by calorimeters, [14] but 46 ± 7 kcal/mol measured with equivalent method in Takacs' study.…”

Section: Introductionmentioning

confidence: 99%

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Density functional theory calculations on S―S bond dissociation energies of disulfides

Yang

Sun

et al. 2015

J of Physical Organic Chem

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The S-S bond cleavage plays an important role in affecting the reactivity or biological activities of disulfide-based compounds. With the aid of density functional theory (DFT) calculations, the present study focuses on predicting the S-S bond dissociation energies (BDEs) of disulfides. The range of BDEs of different types of disulfides was constructed for the first time. It was found that the electronic effect (and especially the conjugation effect) of substituents is predominant in determining the S-S bond strength of disulfides. By contrast, the steric effect is insignificant for most molecules due to the long S-S bond distances. We hope that the present study will benefit the future development of more powerful strategies in activating the S-S bond of disulfides.

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Section: Introductionsupporting

confidence: 86%

Section: Introductionsupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

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Density functional theory calculations on S―S bond dissociation energies of disulfides

Yang

Sun

et al. 2015

J of Physical Organic Chem

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“…Our value of ∆ f H o (FSO 2 ) ϭ Ϫ96.2 Ϯ 3.0 kcal mol Ϫ1 differs strongly from those estimated by Takacs, Ϫ117 Ϯ 5 kcal mol Ϫ1 [13], Sudlow and Woolf, Ϫ110 kcal mol Ϫ1 [17] and Li, Ϫ81.8 kcal mol Ϫ1 [12]. However, within the combined stated errors, our result is in reasonable agreement with the value recommended by Herron of Ϫ102 Ϯ 4 kcal mol Ϫ1 [15].…”

Section: ) 2 Ch3oϩsh2ϩsfϩh2so4supporting

confidence: 73%

Theoretical Study of the Heats of Formation of SF, FSO, FSO2 and HSO Radicals

Badenes¹,

Tucceri²,

Cobos³

2000

Zeitschrift Für Physikalische Chemie

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Heat of Formation / SF / FSO / FSO 2 / HSOStandard heats of formation of SF, FSO, FSO2 and HSO radicals have been calculated with the hybrid B3LYP density functional using extended basis sets and with CBS-4M, CBS-q, CBS-Q and CBS-QB3 model chemistries. The values computed from bond dissociation enthalpies and atomization energies are typically 2Ϫ3 kcal mol Ϫ1 higher than those obtained from a large number of isodesmic reactions. Application of isodesmic reactions calculations with energies computed at the CBS-q level of theory yielded our best values of 0.2Ϯ1.0, Ϫ69.9Ϯ2.0, Ϫ96.2Ϯ3.0, and Ϫ4.4Ϯ1.5 kcal mol Ϫ1 for SF, FSO, FSO2 and HSO respectively. The values for the FSO and FSO2 reduce markedly the literature uncertainties while the values for the SF and HSO are in very good agreement with previous ab initio estimates.

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“…[17] The difference is of similarly large magnitude (41 kcal mol À1 ) in comparing the bond strengths of S À F vs. S À Cl bonds in SO 2 FCl. [18] These factors produce a surprising and highly useful passivity in the -SO 2 F group. A small gem of comparative observation was provided more than 40 years ago by gas chromatography analysis of sulfonyl halides, showing directly the thermal and hydrolytic fragility of RSO 2 Cl compared to RSO 2 F. [19] An even earlier and more striking case from Steinkopf and Jaeger described the Ullmann coupling of iodo-3-fluorosulfonylbenzenes over metallic copper powder at elevated temperatures, without decomposition of the SO 2 F group [Eq.…”

Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

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Heats of formation and bond dissociation energies of some simple sulfur- and halogen-containing molecules

Cited by 32 publications

References 11 publications

Density functional theory calculations on S―S bond dissociation energies of disulfides

Density functional theory calculations on S―S bond dissociation energies of disulfides

Theoretical Study of the Heats of Formation of SF, FSO, FSO2 and HSO Radicals

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

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