An account of chronological computational investigations to ascertain the role of pπ-pπ bonding in influencing the Lewis acidity of BX3 (X = F, Cl, Br and I): Evolution of novel parameters and relegation of π-type back bonding concept

Sinha, Ankita; Banerjee, Suparna; Gangopadhyay, Jaydip

doi:10.1016/j.ccr.2022.214519

Cited by 6 publications

(3 citation statements)

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“…These are useful parameters in understanding the global reactivity and local site selectivity, respectively. To investigate the structure-activity (QSAR), structure-property (QSPR) and structure-toxicity (QSTR) relationships [84] , [85] , [86] , [87] , [88] quantitatively, the reactivity descriptors are used routinely.…”

Section: Resultsmentioning

confidence: 99%

An account of noncovalent interactions in homoleptic palladium(II) and platinum(II) complexes within the DFT framework: A correlation between geometries, energy components of symmetry-adapted perturbation theory and NCI descriptors

Chakraborty¹

2022

Heliyon

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Section: Resultsmentioning

confidence: 99%

An account of noncovalent interactions in homoleptic palladium(II) and platinum(II) complexes within the DFT framework: A correlation between geometries, energy components of symmetry-adapted perturbation theory and NCI descriptors

Chakraborty¹

2022

Heliyon

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“…7 There are a number of explanations for this anomalous trend, each of which differ, at the same time, all makes sense. [8][9][10][11][12] In other words there is no consensus among scientists regarding this. Nevertheless, the basic inorganic textbook explanation based on π back-bonding remains as the widely believed one.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acidity Trend of Boron Trihalides: If Not π Back-Bonding, What Else?

Thayyil

Parambil

2022

Preprint

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Lewis acidity trend of boron trihalides is a subject that has received a variety of explanations, and still the simple π back-bonding based one is believed by most, perhaps because of its simplicity, irrespective of opposing findings. Herein we try to give an alternative explanation based on qualitative Molecular Orbital (MO) theory, and support that quantitatively by Generalized Kohn-Sham Energy Decomposition Analysis. While the role of orbital overlap on the orbital interaction energy is widely known, the role of electronegativity of the atoms involved is often overlooked. Here we find that the Lewis acidity trend of boron and aluminum halides can be explained by the WolfsbergHelmholz (W-H) formula for resonance integral . The MO theory based predictions are valid only when the orbital interactions are strong enough. In the weakly interacting systems the effect of orbital interactions can be overshadowed by other effects such as Pauli repulsion, dispersion etc. Thus the Lewis acidity trend of boron and aluminum halides can vary depending on the strength of interacting Lewis base. We believe that this work would enable one to gain a better understanding not only on the Lewis acidity of boron trihalides and its heavy analogs, but also on a variety of related problems such as the stronger π acidity of CS compared to CO and weaker π bonding between heavy atoms.

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“…[7] There are a number of explanations for this anomalous trend, each of which differs, at the same time, all make sense. [8][9][10][11][12] In other words there is no consensus among scientists regarding this. Nevertheless, the basic inorganic textbook explanation based on π back-bonding remains as the widely believed one.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acidity Trend of Boron and Aluminium Trihalides: If Not π Back‐Bonding, What Else?**

Thayyil

Parambil

2022

ChemPhysChem

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Lewis acidity trend of boron trihalides is a subject that has received a variety of explanations, and still, the simple π backbonding based one is believed by most, perhaps because of its simplicity, irrespective of opposing findings. Herein we try to give an alternative explanation based on qualitative Molecular Orbital (MO) theory and support that quantitatively by Generalized Kohn-Sham Energy Decomposition Analysis. While the role of orbital overlap on the orbital interaction energy is widely known, the role of electronegativity of the atoms involved is often overlooked. Here we find that the Lewis acidity trend of boron and aluminium halides can be explained by the Wolfsberg-Helmholz (WÀ H) formula for resonance integral. The MO theory-based predictions are valid only when the orbital interactions are strong enough. In weakly interacting systems, the effect of orbital interactions can be overshadowed by other effects such as Pauli repulsion, dispersion, etc. Thus the Lewis acidity trend of boron and aluminium halides can vary depending on the strength of the interacting Lewis base. We believe that this work would enable one to gain a better understanding not only on the Lewis acidity of boron trihalides and its heavy analogs but also on a variety of related problems such as the stronger π acidity of CS compared to CO and weaker π bonding between heavy atoms.

show abstract

An account of chronological computational investigations to ascertain the role of pπ-pπ bonding in influencing the Lewis acidity of BX3 (X = F, Cl, Br and I): Evolution of novel parameters and relegation of π-type back bonding concept

Cited by 6 publications

References 356 publications

An account of noncovalent interactions in homoleptic palladium(II) and platinum(II) complexes within the DFT framework: A correlation between geometries, energy components of symmetry-adapted perturbation theory and NCI descriptors

An account of noncovalent interactions in homoleptic palladium(II) and platinum(II) complexes within the DFT framework: A correlation between geometries, energy components of symmetry-adapted perturbation theory and NCI descriptors

Lewis Acidity Trend of Boron Trihalides: If Not π Back-Bonding, What Else?

Lewis Acidity Trend of Boron and Aluminium Trihalides: If Not π Back‐Bonding, What Else?**

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