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

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(...

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Bibliographic Details
Published in:Chemical science (Cambridge) Vol. 13; no. 35; pp. 1532 - 1545
Main Authors: Suhr, Simon, Walter, Robert, Beerhues, Julia, Albold, Uta, Sarkar, Biprajit
Format: Journal Article
Language:English
Published: CAMBRIDGE Royal Soc Chemistry 14.09.2022
Royal Society of Chemistry
The Royal Society of Chemistry
Subjects:
Chemistry
Chemistry, Multidisciplinary
Coordination compounds
Crystallography
Electrochemistry
Ligands
NMR spectroscopy
Oxidation
Physical Sciences
Quantum chemistry
Reactivity
Rhodium
Science & Technology
ELECTROCHEMICAL PROPERTIES
HYDROGEN-ATOM TRANSFER
COBALT COMPLEXES
CHARGE-DISTRIBUTION
ELECTRON-TRANSFER SERIES
MONONUCLEAR RHODIUM(II)
NICKEL(II) COMPLEXES
DONOR-ACCEPTOR SYSTEMS
BOND ACTIVATION
METAL-COMPLEXES
ISSN:2041-6520, 2041-6539
Online Access:Get full text
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Summary: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 O 2 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 [CH 3 ] + 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. Diamidobenzene ligands are versatile platforms in organometallic Rh-chemistry. They allow the isolation of tunable mononuclear ate-complexes, and the formation of a unprecedented homobimetallic, heterovalent complex.
Bibliography:Electronic supplementary information (ESI) available. CCDC
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2177590
For ESI and crystallographic data in CIF or other electronic format see
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https://doi.org/10.1039/d2sc03227a
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ISSN:2041-6520
2041-6539
DOI:10.1039/d2sc03227a