Issue 35, 2022

Rhodium diamidobenzene complexes: a tale of different substituents on the diamidobenzene ligand

Abstract

Diamidobenzene ligands are a prominent class of redox-active ligands owing to their electron reservoir behaviour, as well as the possibility of tuning the steric and the electronic properties of such ligands through the substituents on the N-atoms of the ligands. In this contribution, we present Rh(III) complexes with four differently substituted diamidobenzene ligands. By using a combination of crystallography, NMR spectroscopy, electrochemistry, UV-vis-NIR/EPR spectroelectrochemistry, and quantum chemical calculations we show that the substituents on the ligands have a profound influence on the bonding, donor, electrochemical and spectroscopic properties of the Rh complexes. We present, for the first time, design strategies for the isolation of mononuclear Rh(II) metallates whose redox potentials span across more than 850 mV. These Rh(II) metallates undergo typical metalloradical reactivity such as activation of O2 and C–Cl bond activations. Additionally, we also show that the substituents on the ligands dictate the one versus two electron nature of the oxidation steps of the Rh complexes. Furthermore, the oxidative reactivity of the metal complexes with a [CH3]+ source leads to the isolation of a unprecedented, homobimetallic, heterovalent complex featuring a novel π-bonded rhodio-o-diiminoquionone. Our results thus reveal several new potentials of the diamidobenzene ligand class in organometallic reactivity and small molecule activation with potential relevance for catalysis.

Graphical abstract: Rhodium diamidobenzene complexes: a tale of different substituents on the diamidobenzene ligand

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Jun 2022
Accepted
15 Jul 2022
First published
21 Jul 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 10532-10545

Rhodium diamidobenzene complexes: a tale of different substituents on the diamidobenzene ligand

S. Suhr, R. Walter, J. Beerhues, U. Albold and B. Sarkar, Chem. Sci., 2022, 13, 10532 DOI: 10.1039/D2SC03227A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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