Evaluation of group electronegativity by Pauling's thermochemical method

Datta, Dipankar; Singh, Shweta

doi:10.1021/j100368a083

Cited by 27 publications

(12 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This order differs from the Pauling/Datta scale, where χ (C(CH 3 ) 3 ) is larger than χ (i-C 3 H 7 ) and χ (C 2 H 5 ) due to a spurious steric effect. 11 For other ligands, the broad features generally match those of other methods (e.g., χ (CH 3 ) < χ(CF 3 ), and χ (SiH 3 )<χ (SiCl 3 ) < χ(SiF 3 ), as expected). However, there are a few exceptions, namely C(CH 3 ) 3 , SiH 3 , H, CH 3 , and CF 3 , for which the current approach has the electronegativities increasing in the following order: χ (SiH 3 ) (1.70) < χ(C(CH 3 ) 3 (2.25) < χ(CH 3 ) exp (2.39) < χ(H) exp (2.62) < χ(CF 3 ) exp (3.02), differing somewhat from other approaches such as XPS, Pauling/Datta, and Pearson.…”

Section: B From the Free Radical To The Molecule: Geometry Dependencsupporting

confidence: 74%

“…Several schemes have been proposed over the years, leading to a number of different electronegativity scales. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Historically, three major approaches to electronegativity of atoms and chemical groups have emerged over the last century. In introducing the concept, Linus Pauling defined electronegativity as "the power of an atom in a molecule to attract electrons to itself," 1,2 i.e., the concept of electronegativity was clearly defined in terms of an atom within a molecule.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A new method to derive electronegativity from resonant inelastic x-ray scattering

Carniato

Journel

Guillemin

et al. 2012

The Journal of Chemical Physics

View full text Add to dashboard Cite

Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p(-1)LUMO(1) electronic states reached after Cl 1s → LUMO core excitation and subsequent KL radiative decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2p(z) atomic orbital contributing to the Cl 2p(3/2) molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches.

show abstract

Section: B From the Free Radical To The Molecule: Geometry Dependencsupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

A new method to derive electronegativity from resonant inelastic x-ray scattering

Carniato

Journel

Guillemin

et al. 2012

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Most of the theoretical scales do not correlate well with the two experimental ones. 16,17 Moreover, none of the theoretical methods can accommodate the ionic and the neutral groups on the same basis. With these two aspects in mind, for quite some time we have been trying to devise a suitable theoretical scale for group electronegativity.…”

Section: Calculationsmentioning

confidence: 99%

Electronegativity and Bader's bond critical point

Hati

Datta

1992

J Comput Chem

View full text Add to dashboard Cite

The electronegativities (xp) of some 36 atoms/groups (including some 6 ionic ones) X are calculated from the atomic charges in the corresponding methyl species CHBX that were obtained by applying Bader's theory of atoms in molecules. The numerical values of the XI for the various groups studied are reasonable and correlate linearly with the two existing experimental scales for group electronegativity, Inamoto's i scale and the 'JCC (ortho-ipso) coupling constants in the monosubstituted benzenes, to satisfactory extents. The relations between the x$ values and some "critical properties" of the various CHBX molecules considered are also studied. It is suggested that in a molecule PX, rp/R where rp is the distance of Bader's critical point on the bond PX of length R from the atom P or the binding atom of the group P can be a very good measure of the electronegativity of the atom/group X .

show abstract

“…Group electronegativity is a quite useful concept for explaining and understanding the properties of organic compounds, and its determination was largely divided into the experimental and theoretical approaches. In the experimental methods, it can be obtained from thermochemical data [3], NMR [4], solubility [5], basicity and coupling potential [6], bond dissociation enthalpy [7], or other experimental data of groups, which is credible and also is limited by the experimental condition and the lack of organic compounds to be investigated. To obtain more group electronegativities, many calculation methods including empirical and quantum chemistry were proposed.…”

Section: Introductionmentioning

confidence: 99%

Topological Electronegativity Index and Its Application – I. Ionization Potentials of Alkyl Groups and Alkyl Halides

Cao

Luo

2007

QSAR Comb. Sci.

View full text Add to dashboard Cite

A Topological Electronegativity Index (TEI) for alkyl group was developed, based on the bond adjacency matrix of the radical atom. Taking the radical atom and the adjacency atoms (or groups) as the vertices of molecular graph of the alkyl group, the bond adjacency matrix was constructed, in which the diagonal elements were assigned the Pauling electronegativity of the atom (or group), and the off-diagonal elements were assigned values 1 or 0. The off-diagonal elements represent the bond connections: that is when the two atoms (or groups) connect with each other, it is 1; otherwise is 0. From the matrix, the eigenvalues were obtained and its geometric mean value was considered as the TEI of an alkyl. The calculated TEI has good correlation with its experimental ionization potential. Further, the TEI was applied to correlate with the ionization potentials of alkyl halides and substituted ethenes, and to correlate with the Bond Dissociation Energies (BDEs) of the C i À H bonds in alkanes.

show abstract

Evaluation of group electronegativity by Pauling's thermochemical method

Cited by 27 publications

References 0 publications

A new method to derive electronegativity from resonant inelastic x-ray scattering

A new method to derive electronegativity from resonant inelastic x-ray scattering

Electronegativity and Bader's bond critical point

Topological Electronegativity Index and Its Application – I. Ionization Potentials of Alkyl Groups and Alkyl Halides

Contact Info

Product

Resources

About