Buchhorn, Moritz ; Deeth, Robert J. ; Krewald, Vera (2023)
Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters.
In: Chemistry - A European Journal, 2022, 28 (9)
doi: 10.26083/tuprints-00024313
Artikel, Zweitveröffentlichung, Verlagsversion

Kurzbeschreibung (Abstract)

The properties and reactivities of transition metal complexes are often discussed in terms of Ligand Field Theory (LFT), and with ab initio LFT a direct connection to quantum chemical wavefunctions was recently established. The Angular Overlap Model (AOM) is a widely used, ligand‐specific parameterization scheme of the ligand field splitting that has, however, been restricted by the availability and resolution of experimental data. Using ab initio LFT, we present here a generalised, symmetry‐independent and automated fitting procedure for AOM parameters that is even applicable to formally underdetermined or experimentally inaccessible systems. This method allows quantitative evaluations of assumptions commonly made in AOM applications, for example, transferability or the relative magnitudes of AOM parameters, and the response of the ligand field to structural or electronic changes. A two‐dimensional spectrochemical series of tetrahedral halido metalates ([MIIX₄]²⁻, M=Mn−Cu) served as a case study. A previously unknown linear relationship between the halide ligands’ chemical hardness and their AOM parameters was found. The impartial and automated procedure for identifying AOM parameters introduced here can be used to systematically improve our understanding of ligand–metal interactions in coordination complexes.

Typ des Eintrags:	Artikel
Erschienen:	2023
Autor(en):	Buchhorn, Moritz ; Deeth, Robert J. ; Krewald, Vera
Art des Eintrags:	Zweitveröffentlichung
Titel:	Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters
Sprache:	Englisch
Publikationsjahr:	24 November 2023
Ort:	Darmstadt
Publikationsdatum der Erstveröffentlichung:	2022
Ort der Erstveröffentlichung:	Weinheim
Verlag:	Wiley-VCH
Titel der Zeitschrift, Zeitung oder Schriftenreihe:	Chemistry - A European Journal
Jahrgang/Volume einer Zeitschrift:	28
(Heft-)Nummer:	9
Kollation:	14 Seiten
DOI:	10.26083/tuprints-00024313
URL / URN:	https://tuprints.ulb.tu-darmstadt.de/24313
Zugehörige Links:	Verlags-DOI
Herkunft:	Zweitveröffentlichung DeepGreen
Kurzbeschreibung (Abstract):	The properties and reactivities of transition metal complexes are often discussed in terms of Ligand Field Theory (LFT), and with ab initio LFT a direct connection to quantum chemical wavefunctions was recently established. The Angular Overlap Model (AOM) is a widely used, ligand‐specific parameterization scheme of the ligand field splitting that has, however, been restricted by the availability and resolution of experimental data. Using ab initio LFT, we present here a generalised, symmetry‐independent and automated fitting procedure for AOM parameters that is even applicable to formally underdetermined or experimentally inaccessible systems. This method allows quantitative evaluations of assumptions commonly made in AOM applications, for example, transferability or the relative magnitudes of AOM parameters, and the response of the ligand field to structural or electronic changes. A two‐dimensional spectrochemical series of tetrahedral halido metalates ([MIIX₄]²⁻, M=Mn−Cu) served as a case study. A previously unknown linear relationship between the halide ligands’ chemical hardness and their AOM parameters was found. The impartial and automated procedure for identifying AOM parameters introduced here can be used to systematically improve our understanding of ligand–metal interactions in coordination complexes.
Alternatives oder übersetztes Abstract:	Alternatives Abstract Sprache In Ligand Field Theory, the angular overlap model (AOM) can in principle describe the electron donor/acceptor capabilities of individual ligands. However, its applicability is limited by the nature of the spectroscopic data. We present a computational approach for automated AOM parameter fitting and investigate metal–halide bonds that had previously been described only heuristically. This approach is applied to a 2D spectrochemical series, for which a linear relationship between AOM parameters and the chemical hardness of the ligands is found. Englisch
Freie Schlagworte:	ab initio calculations, angular overlap model, ligand effects, ligand field theory, transition metal complexes
ID-Nummer:	e202103775
Status:	Verlagsversion
URN:	urn:nbn:de:tuda-tuprints-243135
Zusätzliche Informationen:	This article also appears in: Quantum Bioinorganic Chemistry (QBIC)
Sachgruppe der Dewey Dezimalklassifikatin (DDC):	500 Naturwissenschaften und Mathematik > 540 Chemie
Fachbereich(e)/-gebiet(e):	07 Fachbereich Chemie 07 Fachbereich Chemie > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie)
Hinterlegungsdatum:	24 Nov 2023 13:36
Letzte Änderung:	27 Nov 2023 06:29
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Verfügbare Versionen dieses Eintrags

• Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters. (deposited 24 Nov 2023 13:36) [Gegenwärtig angezeigt]
  • Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters. (deposited 05 Jan 2022 07:12)

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