Relationship of QTAIM and NOCV Descriptors with Tolman’s Electronic Parameter

Abstract

The σ-donor properties of various P-donor ligands have been studied at the PBEPBE level of theory, which has proved to be accurate in computing the symmetric carbonyl stretching frequencies in nickel(0)-tricarbonyl complexes containing P-donor ligands. The delocalization index from the QTAIM methodology and the energy component associated with the NOCV deformation density representing the donor interaction give the best correlation with Tolman’s electronic parameters, whereas the electron density at the bond critical point and the Wiberg bond index are connected with the donor strength of the ligands to a lesser extent.

Comprehensive SPHYB and B3LYP-DFT Studies of Two Types of Ferrocene

“…It can also be seen that the most charge is populated around the Cp ring. The electronic structure of ferrocene substituted cavitands is studied by Kegl . Its results show that the tilt angle of the functioned Cp rings strongly influences the electron density distribution.…”

“…A scientific method such as NBO could be performed for understanding the covalent and non‐covalent bonds . For this purpose the compounds I and II considered in three units: central Fe as unit 1 and Cp rings as unit 2 and 3 (see Table ) that the attractive Fe–Cp interactions as a donor‐acceptor one on the basis of the natural atomic charges and the basis of the computed second‐order perturbation energies are analyzed. According to this method the strength of the formed bond through CT between two fragments as donor (D) and acceptor (A) is affected with deformation energy (Δ E deform ) of these fragments and energy of bond formation (Δ E int ).…”

Trans‐philicity (trans‐influence/trans‐effect) ladders for square planar platinum(II) complexes constructed by 35Cl NMR probe

“…Noteworthy in both ladders, the trans ‐philicity of phosphane ligands follows the order: PF 3 > PH 3 > PPh 3 > PMe 3 . It should be noticed that according to the σ ‐donor/ π ‐acceptor ratio, PF 3 , PH 3 and PMe 3 follow the trend PF 3 < PH 3 < PMe 3 , while according to the ν (C ≡ O) stretching vibrational frequencies for Ni(CO) 3 L complexes follow the order PF 3 > PPh 3 > PMe 3 in line with the trans ‐philicity sequence for the phosphane ligands. Similarly, the NMR trans ‐philicity ladders reproduce the experimentally established trans ‐influence/ trans ‐effect sequences: Br − > Cl − > F − and NH 3 > Py.…”

Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman’s Electronic Parameters

“…For the complexes containing conformationally flexible ligands, conformational analyses have been performed in a similar manner reported earlier [26], and the lowest energy species were considered. QTAIM analyses of the wave function [40] were carried out with AIMAll software [41].…”

“…The second category uses approaches that focus on the entire transition-metal complex, thereby including the possibility to scrutinize ligand–ligand effects as well [23]. Various electronic structure methods, such as Extended Transition State theory combined with Natural Orbitals of Chemical Valence (ETS-NOCV) [24,25,26,27] and Quantum Theory of Atoms in Molecules (QTAIM) [26] have been employed as well.…”