Structural effects in octahedral carbonyl complexes: an atoms-in-molecules study

Abstract

We gratefully acknowledge the CRIANN computational center for providing HPC resources, and LABEX SynOrg for support. VT thanks the Centre National de la Recherche Scientifique (CNRS) for a half-time "delegation".International audienceIn this paper, we assess the ability of descriptors defined within the framework of the quantum theory of atoms-in-molecules to retrieve trans and cis structural effects in 42 d(6) octahedral carbonyl organometallic complexes involving cobalt and rhodium atoms. More specifically, correlations between bond lengths in trans or cis position with respect to common orienting ligands and both local (such as molecular electrostatic potential values or the properties of critical points of the electron density Laplacian field) and integrated (over the metal atomic basin, such as multipolar moments, various energy contributions, condensed conceptual DFT quantities) properties are investigated, casting some light on the physicochemical features that drive this fundamental structural effect

Effect of Enhanced Electron Withdrawal on the Cohesion of Cr‐Pd Hemichelates

“…–45 kcal/mol, which contains 89 % of electrostatic attractive character. Similar observations were made by Tognetti et al in homobimetallic carbonyl complexes such as Co 2 (CO) 8 , which led the authors to point out that a great part of the cohesion of such complexes arises from metal‐carbonyl interactions. In both complexes, other interatomic interactions in the Pd coordination sphere, such as N‐Pd, C Ar –Pd and C benz –Pd, are consistently found strongly attractive with a dominating covalence for the two latter ones and a balanced ionic/covalent contribution for the former one.…”

“…The QTAIM‐based Interacting Quantum Atoms energy partitioning method developed by Pendas and co‐workers is a useful tool for investigating noncovalent interactions that has rarely been used to date in the study of transition metal complexes . Based on real‐space partitioning of the molecular space, this method, when extended to the Kohn–Sham DFT framework,, gives access to a partitioning of energy contributions of exchange‐correlation, and a series of coulombic interaction terms for two‐atom interactions within a molecule.…”

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

“…To our knowledge, QTAIM, which relies on the zero-flux boundary condition [35][36][37][38][39][40], is one of the current leading theoretical approaches used to study the nature and strength of hydrogen bonding and other non-covalent interactions. Two of its charge density-based topological descriptors, viz., the presence of a bond path (bp), and the presence of the (3,-1) bond critical point (bcp) between interacting atomic basins have proved very useful in inferring the presence of a chemical bonding in chemical systems [35][36][37][38][39][53][54][55][56][57][58][59][60]. Two of its other signatures, the sign of the Laplacian of the charge density ( 2  b ) and the sign of the total energy density (H b ) at a bcp, can be used (and have been recommended) to determine whether the interaction between two atomic basins in a given pair is ionic, covalent, or a mixture of the two [59][60][61][62][63][64][65].…”

On Atoms‐in‐Molecules Energies from Kohn–Sham Calculations

“…The model IQA approach proved to be the most promising because it is not biased by the uniform scaling procedure and showed a high correlation with the experimental rate constants and with the complexation energies, going beyond the pure electrostatic model embodied by the σ‐hole concept. Such preliminary results constitute, from our point of view, a strong incentive to foster the use of IQA energy decomposition analysis for other systems (e.g., organometallic ones) and reactivity issues.…”