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Heteroleptic Dirhodium(II) Complexes with Redox‐Active Ferrocenyl Ligands: Synthesis, Electrochemical Properties, and Redox‐Responsive Chemoselectivity in Carbene C−H Insertion
Author(s) -
Ruzhylo Illia,
SourniaSaquet Alix,
Moreau Alain,
Delord Tom,
Manoury Eric,
Poli Rinaldo,
Labande Agnès
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202200033
Subject(s) - chemistry , chemoselectivity , redox , ligand (biochemistry) , carbene , medicinal chemistry , cyclic voltammetry , diazo , electrochemistry , intramolecular force , stereochemistry , combinatorial chemistry , catalysis , organic chemistry , biochemistry , receptor , electrode
A series of original heteroleptic dirhodium(II) complexes ( 4 a–j ) of formula [Rh 2 (OAc) 3 (L)], where L is a redox‐active ferrocenecarboxylate ligand, has been prepared. These dirhodium(II) complexes have been characterised by NMR, mass spectrometry and cyclic voltammetry. All complexes show a quasi‐reversible redox behaviour for the ferrocenyl unit. The latter can be selectively oxidised by [N(4‐C 6 H 4 Br) 3 ] + BF 4 − . Four selected heteroleptic complexes 4 a, 4 b , 4 f and 4 i , have been evaluated as catalysts for the intramolecular decomposition of a diazo compound 5 . The ratio between the aromatic substitution product 6 and the aliphatic C−H insertion product 7 increases (up to 19 % increase) when using the in situ generated oxidised form of the dirhodium(II) complexes ( 4 a + BF 4 − to 4 i + BF 4 − ). This shows that the oxidation of the ferrocenecarboxylate ligand has an effect on the chemoselectivity of the dirhodium‐catalysed diazo decomposition, and thus that the electronic properties of a complex can be tuned without exchanging ligands.