Polarity of organometallic systems: Correlation analysis via substituent constants

Egorochkin, A. N.; Кузнецова, О. В.; Хамалетдинова, Н. М.; Domratcheva‐Lvova, Lada

doi:10.1016/j.ica.2017.10.021

Cited by 15 publications

(3 citation statements)

References 47 publications

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“…Despite not being actively involved in reactions, substituents play vital roles in affecting the reactivity and properties of molecules. − They modulate kinetics and thermodynamics of reactions . Due to their importance, the development of physically meaningful descriptors describing substituent properties is vital for use in quantitative structure–property relationships (QSPR).…”

Section: Introductionmentioning

confidence: 99%

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Lefrancois-Gagnon,

Mawhinney

2023

J. Chem. Inf. Model.

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Substituents modulate reactions, but their effects are commonly described by using proxies to their functional group properties. Substituent descriptors from the quantum theory of atoms in molecules, which are true functional group properties, are related here to these proxies, which have historically had chemically relevant meaning. Due to the large number of descriptors, multivariate analysis is used to intuit their significance. Multiple linear regression, principal component, and partial least squares regression analyses highlight that these substituent descriptors contain similar information to the proxies while being intrinsic, predictable substituent properties. Sources of error limiting quantitative reproduction of the proxy data include transferability, experimental accuracy, and solvation issues.

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Section: Introductionmentioning

confidence: 99%

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Lefrancois-Gagnon,

Mawhinney

2023

J. Chem. Inf. Model.

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“…Variations in the electron‐donating groups (EDGs) and electron‐withdrawing groups (EWGs) of molecules are effective on different physical and chemical properties. Computational investigations of substituent effects on the structure and properties of the molecules have been reported 39–68 …”

Section: Introductionmentioning

confidence: 99%

Computational investigation of the substituent effect in the [2 + 4] Diels–Alder cycloaddition reactions of HSi≡Si(para‐C₆H₄X) with benzene

Ahraminejad

Ghiasi

Mohtat

et al. 2021

J Chinese Chemical Soc

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In this paper, the DFT method was applied at the B3LYP/6-311+G (d,p) level of theory to investigate the [2 + 4] Diels−Alder cycloaddition reactions of HSi≡Si(para-C 6 H 4 X); X = NH 2 , OH, Me, H, F, CCH, OCF 3 with benzene. It was attempted to show how the substituent affects the barrier height and thermodynamic parameters of these reactions. To illustrate the interaction between two fragments at transition states Activation Strain Model (ASM) and Energy Decomposition Analysis (EDA) were utilized. The Wiberg bond indices were used to check the progress of the reactions. The rate constant of the reaction was computed at 300 K, in the gas phase. Also, the synchronicity values of this reaction were determined. K E Y W O R D S rhenabenzyne, phosphine ligand, natural bond analysis (NBO), Tolman cone angles, Tolman's electronic parameter (TEP), para-delocalization index (PDI)

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“…In various investigations, the effect of substituents on the thermal properties, [24] molecular conformations, [25] rates of nucleophilic substitutions and elimination reactions, [26] framework of material science, [27,28] absorption bands of electronic spectra, [29][30][31] and NMR chemical shifts. [32][33][34] Computational studies are useful methods to illustration of the substituent effect on the electronic, structural and spectroscopic properties in the different molecules [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] have been studied.…”

Section: Introductionmentioning

confidence: 99%

Hammett and Brown correlations in the structure and electronic properties of H₂Si=SiHAr (Ar = p‐C₆H₄X; X = NH₂, OH, Me, H, F, Cl, CHO, COOH, CN, NO₂) molecules

Samavat

Ghiasi

Mohtat

2020

J Chinese Chemical Soc

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Substituent effect on the structure and electronic properties of H2Si=SiHAr (Ar = p‐C6H4X; X = NH2, OH, Me, H, F, Cl, CHO, COOH, CN, NO2) molecules are studied at the CAM‐B3LYP/6‐311G(d,p) level of theory. Energy decomposition analysis (EDA) is used as a useful tool for illustrating the interaction between H2Si and SiHAr fragments in HArSi=SiH2 molecules. Energetic analysis reveals that the singlet state of the fragments is more stable than triplet state. Also, interactions are stronger in the presence of electron‐withdrawing groups (EWGs) in comparison to electron donating groups (EDGs). EDG and EDG effects are investigated on the stability of fragments, frontier orbital energy, distortion, HOMO–LUMO gap, electron‐donating (ω−) and electron‐accepting (ω+) powers of the studied molecules. Then, the correlations between these calculated parameters with the Hammett and Brown constants (σp and σp+, respectively) are provided. Also, time‐dependent density functional theory method (TD‐DFT) is employed for the determination of the strongest absorption band values (λmax,el) of these molecules. This absorption band is attributed to the HOMO →LUMO transition.

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Polarity of organometallic systems: Correlation analysis via substituent constants

Cited by 15 publications

References 47 publications

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Computational investigation of the substituent effect in the [2 + 4] Diels–Alder cycloaddition reactions of HSi≡Si(para‐C₆H₄X) with benzene

Hammett and Brown correlations in the structure and electronic properties of H₂Si=SiHAr (Ar = p‐C₆H₄X; X = NH₂, OH, Me, H, F, Cl, CHO, COOH, CN, NO₂) molecules

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Polarity of organometallic systems: Correlation analysis via substituent constants

Cited by 15 publications

References 47 publications

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Toward Universal Substituent Constants: Relating QTAIM Functional Group Descriptors to Substituent Effect Proxies

Computational investigation of the substituent effect in the [2 + 4] Diels–Alder cycloaddition reactions of HSi≡Si(para‐C6H4X) with benzene

Hammett and Brown correlations in the structure and electronic properties of H2Si=SiHAr (Ar = p‐C6H4X; X = NH2, OH, Me, H, F, Cl, CHO, COOH, CN, NO2) molecules

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Computational investigation of the substituent effect in the [2 + 4] Diels–Alder cycloaddition reactions of HSi≡Si(para‐C₆H₄X) with benzene

Hammett and Brown correlations in the structure and electronic properties of H₂Si=SiHAr (Ar = p‐C₆H₄X; X = NH₂, OH, Me, H, F, Cl, CHO, COOH, CN, NO₂) molecules