Thermodynamic Treatments of Lewis Basicity

Gal, Jean‐François

doi:10.1002/9783527675142.ch3

Cited by 2 publications

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“… a The values are in kJ/mol. b Reference . c Reference . d Reference . e Reference . f Reference . g Reference . …”

Section: Resultsmentioning

confidence: 99%

“…Previous studies show that the tendency of the cations to interact covalently with the molecules decreases as H + > CH 3 + > Cu + > Al + ≈ Li + > Na + > K + . 19,26,28 In the covalent interactions, an empty orbital of the cation (Lewis acid) accommodates the LP electron of the Lewis base, and the LP/ BP repulsion is reduced. On the other hand, in highly electrostatic interactions, the charge/dipole dominates and a large part of the LP repulsion remains operative.…”

Section: Introductionmentioning

confidence: 99%

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On the Significance of Lone Pair/Lone Pair and Lone Pair/Bond Pair Repulsions in the Cation Affinity and Lewis Acid/Lewis Base Interactions

Valadbeigi

Gál

2018

ACS Omega

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Interaction of H 2 O, H 2 S, H 2 Se, NH 3 , PH 3 , and AsH 3 with cations H + , CH 3 + , Cu + , Al + , Li + , Na + , and K + was studied from the energetic and structural viewpoint using B3LYP/6-311++G(d,p) method. The charge transfer from the Lewis bases to the cations reduces lone pair/lone pair (LP/LP) repulsion in H 2 O, H 2 S, and H 2 Se and LP/bond pair (LP/BP) repulsion in NH 3 , PH 3 , and AsH 3 . In parallel, changes in the H–M–H angles (M = O, S, Se, N, P, and As) are observed. The change in the H–M–H angle during the interactions was proportional to the amount of charge transferred from the bases to the cations and electron density (ρ) at the molecule/cation bond critical point. Also, the opposite trend for proton affinities of these two families, that is, NH 3 > PH 3 > AsH 3 and H 2 O < H 2 S < H 2 Se, was interpreted on the basis of LP/BP repulsion in their neutral and protonated forms. Interaction of the Lewis bases with neutral Lewis acids including BeH 2 , BeF 2 , and BH 3 was studied energetically and structurally. The calculated energies for interactions of H 2 O and NH 3 with BeH 2 , BeF 2 , and BH 3 are larger than the corresponding values for H 2 S, H 2 Se, PH 3 , and AsH 3 . This difference was interpreted on the basis of the lower stability of H 2 O and NH 3 because of large LP/LP and LP/BP repulsion in H 2 O and LP/BP repulsion in NH 3 .

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