Conjugation of Methylsulfonyl and Nitro Groups with the Mercapto Group in Thiophenols<sup>1</sup>

Bordwell, F. G.; Andersen, Hans M. K.

doi:10.1021/ja01119a069

Cited by 55 publications

(20 citation statements)

References 5 publications

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“…The correlation coefficients are 1.00 (48.9%EtOH, acid–base titration) (Table , Fig. ), 0.99(95.0%EtOH, acid–base titration), 1.00(48%EtOH/H 2 O, acid–base titration), 0.99(MeOH, radiometer titrograph), and 1.00(H 2 O, spectrophotometric method) …”

Section: Resultsmentioning

confidence: 92%

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Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Zeng

Han

et al. 2013

J. Phys. Org. Chem.

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The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of para‐substituted phenoxydicarbonyl(η5‐cyclopentadienyl) iron [p‐G‐C6H4O(η5‐C5H5)Fe(CO)2, abbreviated as p‐G‐C6H4OFp (1), where G = NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO, and NMe2] and para‐substituted benzenethiolatodicarbonyl(η5‐cyclopentadienyl) iron [p‐G‐C6H4S(η5‐C5H5)Fe(CO)2, abbreviated as p‐G‐C6H4SFp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔHhet(Fe–O)'s and ΔHhet(Fe–S)'s. The excellent linear free‐energy relations [r = 0.99 (g, 1a), 1.00 (g, 2b)] among the ΔΔHhet (Fe–O)'s and Δpka's of O–H bonds of p‐G‐C6H4OH or ΔΔHhet(Fe‐S)'s and Δpka's of S–H bonds of p‐G‐C6H4SH imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = −0.99 (g, 1g), −0.98 (g, 2h)] among the ΔΔHhet (Fe‐O)'s or ΔΔHhet(Fe‐S)'s and the substituent σp− constants show that these correlations are in accordance with Hammett linear free‐energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔHhet(Fe–O)'s or ΔHhet(Fe–S)'s. ΔΔHhet(Fe–O)'s(g) (1) and ΔΔHhet(Fe–S)'s(g)(2) follow the Capto‐dative principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 92%

“…The substituent effects [ΔΔ H het (Fe–S)'s] of the theoretical Fe–S heterolytic energies for series 2 calculated by the TPSSTPSS/6‐311 + G(d,p)//B3LYP/6‐31G(d) method are also correlated with other Δp K a 's of S–H bonds of p ‐G‐C 6 H 4 SH . The correlation coefficients are 1.00 (48.9%EtOH, acid–base titration) (Table , Fig.…”

Section: Resultsmentioning

confidence: 94%

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Zeng

Han

et al. 2013

J. Phys. Org. Chem.

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“…The substituent effects [ΔΔ H het (Fe–S)'s] of the theoretical Fe–S heterolytic energies for series 2 calculated by the B3LYP/6‐311 + G(d,p)//B3LYP/6‐31G(d) method are also correlated with other Δp K a 's of S–H bonds of m ‐G‐C 6 H 4 SH . The correlation coefficients are 0.97(48.9%EtOH and acid‐base titration), 0.99(95.0%EtOH and acid‐base titration), 0.99(48%EtOH/H 2 O and acid‐base titration; Fig.…”

Section: Resultsmentioning

confidence: 97%

“…, there are 11 data points in 1 e because Fujio measured 11 δΔ G 0 's of m ‐G‐C 6 H 4 OH by the ion cyclotron resonance equilibrium constant method successfully . Reversely, there are only 6 data points in 2 f because Bordwell determined 6 p K a 's of S–H bonds for m ‐G‐C 6 H 4 SH in 48% EtOH/H 2 O …”

Section: Resultsmentioning

confidence: 99%

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Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and m‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅)

Zeng

Wang

et al. 2016

J of Physical Organic Chem

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The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of (meta‐substituted phenoxy)dicarbonyl(η5‐cyclopentadienyl) iron [m‐G‐C6H4OFp (1)] and (meta‐substituted benzenethiolato)dicarbonyl(η5‐cyclopentadienyl) iron [m‐G‐C6H4SFp (2)] complexes. In this study, Fp is (η5‐C5H5)Fe(CO)2, and G is NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO, and NMe2. The results show that Tao–Perdew–Staroverov–Scuseria and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔHhet(Fe–O)'s and ΔHhet(Fe–S)'s. The excellent linear free energy relations [r = 1.00 (g, 1e), 1.00 (g, 2b)] among the ΔΔHhet (Fe–O)'s and δΔG0 of OH bonds of m‐G‐C6H4OH or ΔΔHhet(Fe–S)'s and ΔpKa's of SH bonds of m‐G‐C6H4SH imply that the governing structural factors for these bond scissions are similar. And, the linear correlations [r = −0.97 (g, 1 g), −0.97 (g, 2 h)] among the ΔΔHhet (Fe–O)'s or ΔΔHhet(Fe–S)'s and the substituent σm constants show that these correlations are in accordance with Hammett linear free energy relationships. The inductive effects of these substituents and the basis set effects influence the accuracy of ΔHhet(Fe–O)'s or ΔHhet(Fe–S)'s. The ΔΔHhet(Fe–O)'s(g) (1) and ΔΔHhet(Fe–S)'s(g)(2) follow the capto‐dative Principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2016 John Wiley & Sons, Ltd.

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TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

Bergmann¹,

Ginsburg

Pappo

2011

Organic Reactions

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The Michael condensation in its original scope is the addition of an addend or donor containing an alpha‐hydrogen atom in the system OCCH to a carbon‐carbon double bond that forms part of a conjugated system of the general formula CCCO in an acceptor. The condensation takes place under the influence of alkaline reagents, typically alkali metal alkoxides. The range of addends is very broad. Typical acceptors are alpha, beta‐unsaturated aldehydes, keotnes, and acid derivatives. As an extension of the original scope, the Michael condensation has come to be understood to include addends and acceptors activated by groups other than carbonyl and carboxalkoxy. The wider scope is encompassed in this survey.

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Conjugation of Methylsulfonyl and Nitro Groups with the Mercapto Group in Thiophenols¹

Cited by 55 publications

References 5 publications

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and m‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅)

TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

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Conjugation of Methylsulfonyl and Nitro Groups with the Mercapto Group in Thiophenols1

Cited by 55 publications

References 5 publications

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C6 H4 OFe(CO)2 (η 5 -C5 H5 ) and p -G-C6 H4 SFe(CO)2 (η 5 -C5 H5 )

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C6 H4 OFe(CO)2 (η 5 -C5 H5 ) and p -G-C6 H4 SFe(CO)2 (η 5 -C5 H5 )

Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5)

TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

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Conjugation of Methylsulfonyl and Nitro Groups with the Mercapto Group in Thiophenols¹

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C₆ H₄ OFe(CO)₂ (η ⁵ -C₅ H₅ ) and p -G-C₆ H₄ SFe(CO)₂ (η ⁵ -C₅ H₅ )

Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and m‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅)