Recent progress in quantifying substituent effects

Cao, Chenzhong; Wu, Yaxin

doi:10.1007/s11426-013-4890-0

Cited by 20 publications

(20 citation statements)

References 119 publications

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“…Compound b The values were taken from Hansh et al [27] c The values were taken from previous studies. [28][29][30][31][32][33] d Indicator variable of 4′-OH.…”

Section: Figurementioning

confidence: 99%

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Cao

Cheng

Zhang

et al. 2018

J of Physical Organic Chem

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Effect of substituents on the ultraviolet (UV) spectra of supermolecular system involving silver nanoparticles (AgNPs) and Schiff bases was investigated. AgNPs and 49 samples of model compounds (MC), bi-aryl Schiff bases containing hydroxyl (XBAY, involving 4-OHArCH¼NArY, 2-OHArCH¼NArY, XArCH¼NAr-4′-OH, and XArCH¼NAr-2′-OH), were synthesized. The size of AgNPs was characterized by transmission electron microscopy (TEM), and the UV absorption spectra of AgNPs, XBAYs, and MC-AgNPs mixed solutions were measured, respectively. The results show that (1) the size of AgNPs is larger in MC-AgNPs solutions than that in AgNPs solution due to the distribution of MC molecules on the surface of AgNPs; (2) the UV absorption wavelength of XBAYs changes in the action of AgNPs and their wavelength shift exists limitation between XBAY and MC-AgNPs solutions; and (3) the wavelength shift limit of MC-AgNPs (λ WSL ) is influenced by the substituents X and Y and the position of hydroxyl OH. The wavenumber Δν WSL of λ WSL can be quantified by employing the excited-state substituent constant σ ex CC and Hammett constant σ of substituents X and Y. Comparing with the 4-OH, the 4′-OH makes the Δν WSL a red shift, whereas the 2′-OH, comparing with the 2-OH, makes the Δν WSL a blue shift.

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“…Compound b The values were taken from Hansh et al [27] c The values were taken from previous studies. [28][29][30][31][32][33] d Indicator variable of 4′-OH.…”

Section: Figurementioning

confidence: 99%

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Cao

Cheng

Zhang

et al. 2018

J of Physical Organic Chem

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“…The σ α values are calculated by quantum‐chemical methods, normalized to the σ I , σ R , σ R + , and σ R − constants of substituents X, and tabulated for many X . (A somewhat different approach to the problem of polarizability effect is taken by Cao …”

Section: Calculation Procudurementioning

confidence: 99%

“…[29][30][31] (A somewhat different approach to the problem of polarizability effect is taken by Cao. [33,34] ) In non-classic series XBR C q and XR C q , the substituent X and the charged center R C q are spaced closely. This can give rise to the steric effect.…”

Section: Calculation Procudurementioning

confidence: 99%

Bond dissociation energies in organometallic systems: substituent effects

Кузнецова

Egorochkin

Хамалетдинова

et al. 2014

J. Phys. Org. Chem.

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A knowledge of the factors determining the magnitude of the bond dissociation enthalpy (BDE) is of importance to the advancement of theoretical organometallic chemistry and from the practical standpoint. The central atom and the substituents bound to it influence the BDE values; however, the interplay between the BDE and the substituent effects remains unknown. In this work, the literature data on substituent influence on the BDE of lithium, sodium, copper, silver, mercury, aluminium, gallium, silicon, germanium, tin, lead, phosphorus, antimonium, chromium, iron, cobalt, nickel, rhodium, and iridium compounds (37 series) have been analyzed, using the correlation analysis. Generally, the BDE values were first established to depend on the joint influence of the inductive, resonance, polarizability, and steric effects of substituents. The contribution of the polarizability effect ranges up to about 40%. Copyright © 2014 John Wiley & Sons, Ltd.

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“…Two sets of trends were observed. The first trend showed that, for each metal, as the estimated electronegativity [26][27][28][29] of the monodentate ligands increased, the M-C bond lengths tended to decrease. The M-L bond lengths did not follow this trend (Table 3), but as the monodentate ligands are not as geometrically constrained, their modeled bond lengths may be less rigorously predicted.…”

Section: Effect Of Monodentate Ligandmentioning

confidence: 99%

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

Ellis

Downey

2016

Int J of Quantum Chemistry

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New group 10 metalloorganic complexes are proposed as the basis of new catalysts for the formation of carbon‐phosphorous bonds. Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06 analysis predicts a robust planar geometry, regardless of alteration of major components. Precursors for rapid catalyst generation should begin with an electron‐withdrawing monodentate ligand. Palladium and platinum catalysts have lower chemical hardness, but the electron distribution in the HOMO of the nickel‐based catalyst is preferred for reductive catalytic mechanisms. Both electron density and chemical hardness, however, are affected by the choice of metal ion and the composition of the monodentate ligand bound to it. Group 10 metalloorganic complexes are modeled as precursors for generating new catalysts for a minimally wasteful method of forming bonds commonly found in biochemically active compounds. Suitable precursors have an accessible metal center, as well as significant the HOMO/LUMO involvement at the metal center. All complexes studied offer similar geometries, but precursor transformation into catalyst depends on the electron‐withdrawing ligand being exchanged. Catalyst turn over number is predicted to depend primarily on the central metal. © 2016 Wiley Periodicals, Inc.

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Recent progress in quantifying substituent effects

Cited by 20 publications

References 119 publications

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Bond dissociation energies in organometallic systems: substituent effects

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

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