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, 2023, 62 (25)
doi: 10.26083/tuprints-00024321
Article, Secondary publication, Publisher's Version

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Item Type:

Article

Type of entry:

Secondary publication

Title:

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

Language:

English

Date:

4 August 2023

Place of Publication:

Darmstadt

Year of primary publication:

2023

Publisher:

Wiley-VCH

Journal or Publication Title:

Angewandte Chemie International Edition

Volume of the journal:

Issue Number:

Collation:

5 Seiten

DOI:

10.26083/tuprints-00024321

Corresponding Links:

Origin:

Secondary publication DeepGreen

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

Status:

Publisher's Version

URN:

urn:nbn:de:tuda-tuprints-243213

Additional Information:

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

Classification DDC: