Competitive Activation of a Methyl C−H Bond of Dimethylformamide at an Iridium Center

Abstract

During the synthesis of [AsPh_4][Ir(CO)_2I_3Me] by refluxing IrCl_3·3H_2O in DMF (DMF = dimethylformamide) in the presence of aqueous HCl, followed by sequential treatment with [AsPh_4]Cl, NaI, and methyl iodide and finally recrystallization from methylene chloride/pentane, three crystalline byproducts were obtained: [AsPh4]_2[Ir(CO)I_5], [AsPh_4]_2[trans-Ir(CO)I_4Cl], and [AsPh_4][Ir(CO)(κ^2O,C-CH_2NMeCHO)Cl_2I]. The last of these, whose structure (along with the others) was determined by X-ray diffraction, results from activation of a methyl C−H bond of dimethylformamide, rather than the normally much more reactive aldehydic C−H bond.

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