Thermal decomposition of bis[carbonyl(?-alkyl(aryl)thio)?5-cyclopentadienyliron] complexes

Nechitailo, N. A.; Dzyubina, M. A.; Tyurin, V. D.; Muratov, A. N.; Sideridu, A. Ya.; Nekhaev, A. I.

doi:10.1007/bf00955848

Cited by 2 publications

(2 citation statements)

References 6 publications

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“…(Para‐substituted benzenethiolato)dicarbonyl( η 5 ‐cyclopentadienyl) iron ( p ‐G‐C 6 H 4 S( η 5 ‐C 5 H 5 )(CO) 2 Fe, abbreviated as p ‐G‐C 6 H 4 SFp, where G = NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 ) complexes constitute an important class of compounds and have received considerable attention particularly because of their involvement in many synthetic processes. For example, the simple metallothioether FpSPh is obviously a good ligand for mimicking the real, complicated metallothioether ligand Cys‐SFe 4 S 4 (SCys) 3 in the H cluster of [Fe]H 2 ases .…”

Section: Introductionmentioning

confidence: 99%

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Zeng

Dong

et al. 2013

J of Physical Organic Chem

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Metal-ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe-O and Fe-S homolytic bond dissociation energies [ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s] of two series of para-substituted phenoxydicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 OFp (1)] and (para-substituted benzenethiolato)dicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 SFp (2)] were studied using Hartree-Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is (h 5 -C 5 H 5 )Fe(CO) 2 , and G are NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that DFT methods can provide the best price/performance ratio and accurate predictions of ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s. The remote substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s [ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s] can also be satisfactorily predicted. The good correlations [r = 0.98 (g, 1), 0.98 (g, 2)] of ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s in series 1 and 2 with the substituent s p + constants imply that the para-substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH homo (Fe-O)'s (1) and ΔΔH homo (Fe-S)'s (2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes.

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Section: Introductionmentioning

confidence: 99%

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Zeng

Dong

et al. 2013

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…(Para‐substituted benzenethiolato)dicarbonyl( η 5 ‐cyclopentadienyl)iron ( p ‐G‐C 6 H 4 S( η 5 ‐C 5 H 5 )(CO) 2 Fe, abbreviated as p ‐G‐C 6 H 4 SFp, where G = NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO,, and NMe 2 ) complexes constitute an important class of compounds and have received considerable attention particularly because of their involvement in many synthetic processes. For example, p ‐G‐C 6 H 4 SFp (G = NO 2 , CF 3 , Cl, H,, and MeO) reacts with MeI in polar solvents at room temperature (abbreviated as r.t.) to give the corresponding thioether complexes p ‐G‐C 6 H 4 SMe, which under more vigorous conditions undergoes nucleophilic substitution by the iodide anion to give the free thioether and FpI …”

Section: Introductionmentioning

confidence: 99%

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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Thermal decomposition of bis[carbonyl(?-alkyl(aryl)thio)?5-cyclopentadienyliron] complexes

Cited by 2 publications

References 6 publications

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

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 )

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Thermal decomposition of bis[carbonyl(?-alkyl(aryl)thio)?5-cyclopentadienyliron] complexes

Cited by 2 publications

References 6 publications

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

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 )

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Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

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 )