Fine‐Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand‐Ligand‐Cooperativity

Elvers, Benedict J. ; Pätsch, Sebastian ; Bandaru, Siva S. M. ; Krewald, Vera ; Schulzke, Carola ; Fischer, Christian (2023)
Fine‐Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand‐Ligand‐Cooperativity.
In: Angewandte Chemie International Edition, 62 (25)
doi: 10.1002/anie.202303151
Artikel, Bibliographie

Dies ist die neueste Version dieses Eintrags.

Kurzbeschreibung (Abstract)

Heteroleptic molybdenum complexes bearing 1,5‐diaza‐3,7‐diphosphacyclooctane (P₂N₂) and non‐innocent dithiolene ligands were synthesized and electrochemically characterized. The reduction potentials of the complexes were found to be fine‐tuned by a synergistic effect identified by DFT calculations as ligand‐ligand cooperativity via non‐covalent interactions. This finding is supported by electrochemical studies combined with UV/Vis spectroscopy and temperature‐dependent NMR spectroscopy. The observed behavior is reminiscent of enzymatic redox modulation using second ligand sphere effects.

Typ des Eintrags:

Artikel

Erschienen:

2023

Autor(en):

Elvers, Benedict J. ; Pätsch, Sebastian ; Bandaru, Siva S. M. ; Krewald, Vera ; Schulzke, Carola ; Fischer, Christian

Art des Eintrags:

Bibliographie

Titel:

Fine‐Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand‐Ligand‐Cooperativity

Sprache:

Englisch

Publikationsjahr:

2023

Ort:

Darmstadt

Verlag:

Wiley-VCH

Titel der Zeitschrift, Zeitung oder Schriftenreihe:

Angewandte Chemie International Edition

Jahrgang/Volume einer Zeitschrift:

(Heft-)Nummer:

Kollation:

5 Seiten

DOI:

10.1002/anie.202303151

Zugehörige Links:

Kurzbeschreibung (Abstract):

Alternatives oder übersetztes Abstract:

Alternatives Abstract

Sprache

Ligand-ligand cooperativity is introduced as a novel option for fine-tuning redox properties of molecular complexes. The effect was found when combining dithiolene and 1,5-diaza-3,7-diphosphacyclooctane ligands in one complex. During electrochemical measurements, a non-covalent interaction in the second ligand-sphere results in an electronic conversation between both ligands, which has an unprecedented impact on the observed redox transitions.

Englisch

Freie Schlagworte:

Ligand-Ligand Cooperativity, Non-Innocence Ligands, Noncovalent Interactions, Redox Chemistry

ID-Nummer:

e202303151

Zusätzliche Informationen:

Dedicated to Professor Joachim Heinicke valuing his lifetime achievement in phosphorous and nitrogen-based chemistry.

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: