We describe a stepwise synthesis of the hydrido, N-heterocyclic dicarbene iridium(III) pincer complex [Ir(H)I(CNHCCCaNHC)(NCMe)] (3) which features a combination of normal and abnormal NHC ligands. The reaction of the bis(imidazolium) diiodide [(CHimidCHCHimid)]I2 (1) with [Ir(μ-Cl)(cod)]2 afforded first the mono-NHC Ir(I) complex [IrI(cod)(CHimidCHCNHC)]I (2), which was then reacted with 2 equiv. of Cs2CO3 in acetonitrile at 60 °C for 40 h to yield 3. These observations support our previously proposed mechanism for the formation of hydrido, N-heterocyclic dicarbene iridium(III) pincer complexes from the reaction of bis(imidazolium) salts with weak bases involving a mono-NHC Ir(I) intermediate. We describe the reactivity of the mono-NHC Ir(I) complex 2 under various conditions. By changing the reaction solvent from MeCN to toluene, we observed the cleavage of the imidazol-2-ylidene ring and the formation of an iminoformamide-containing mono-NHC Ir(I) complex [IrI(cod){[NHCH
CHN(Ad)CHO]CHCNHC}] (4). Complex 4 was also prepared in high yield from the reaction of 2 with strong bases (potassium tert-butoxide or potassium hexamethyldisilazane), via the initial formation of the complex [IrI(cod)(CHNHCCHCNHC)] (5), which contains a coordinated NHC moiety and a free carbene arm, followed by subsequent hydrolysis of the latter. The bis(imidazolium) salt 1 can be deprotonated by strong bases to form the bis(carbene) ligand CNHCCHCNHC (6), which readily reacts with [Ir(μ-Cl)(cod)]2 to give the dinuclear complex [{IrI(cod)}2(μ-CNHCCHCNHC)] (7), in which the N-heterocyclic bis(carbene) ligand bridges the two metals through the carbene carbon atoms.
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