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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
Article, Bibliographie

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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.

Item Type: Article
Erschienen: 2023
Creators: Elvers, Benedict J. ; Pätsch, Sebastian ; Bandaru, Siva S. M. ; Krewald, Vera ; Schulzke, Carola ; Fischer, Christian
Type of entry: Bibliographie
Title: Fine‐Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand‐Ligand‐Cooperativity
Language: English
Date: 2023
Place of Publication: Darmstadt
Publisher: Wiley-VCH
Journal or Publication Title: Angewandte Chemie International Edition
Volume of the journal: 62
Issue Number: 25
Collation: 5 Seiten
DOI: 10.1002/anie.202303151
Corresponding Links:
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.

Alternative Abstract:
Alternative abstract Language

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.

English
Uncontrolled Keywords: Ligand-Ligand Cooperativity, Non-Innocence Ligands, Noncovalent Interactions, Redox Chemistry
Identification Number: e202303151
Additional Information:

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

Classification DDC: 500 Science and mathematics > 540 Chemistry
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie)
Date Deposited: 02 Aug 2024 12:54
Last Modified: 02 Aug 2024 12:54
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