Preparation of Rhodium(III) Di-NHC Chelate Complexes Featuring Two Different NHC Donors via a Mild NaOAc-Assisted C–H Activation
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Two molecules of 4,5-dichloroimidazole react with dibromomethane to give the diimidazole 1. Reaction of 1 with iodomethane or 2-fluorobenzyl bromide yields the monoalkylated imidazolium/imidazole salts [2]I and [3]Br, respectively. Salt [2]I reacts with Ag2O followed by transmetalation to [Rh(Cp*)(Cl)2]2 to give the RhIII-NHC complex [4], bearing an NHC ligand with a pendant imidazole group. The pendant imidazole can be deprotonated using NaOAc to yield complex [5], bearing a doubly C-metalated C∧C chelate ligand. Reaction of [2]I or [3]Br with NaOAc and [Rh(Cp*)(Cl)2]2 yields the C∧C chelate complexes [7] and [9], respectively, in a one-pot reaction. The imine ring nitrogen atom in complexes [7] and [9] can be protonated using HBF4·Et2O to give complexes [8]BF4 and [11]BF4, each bearing a C(NHC)∧C(pNHC) chelate ligand (pNHC = protic NH,NR-NHC ligand). Alkylation of the imine ring nitrogen atom in [9] yields complex [10]BF4, bearing a unique unsymmetrical (NHC)∧C(NHC′) chelate ligand.
