Formation of Coordinated Nitrosamines by Reaction of K[IrCl₅NO] with Primary Amines

In the present work we describe the formation of primary aromatic and aliphatic coordinated nitrosamines by reaction of the extremely reactive K[IrCl5NO] with p-toluidine and 2,2,2-trifluoroethylamine, respectively. After the counteranion of the product was changed to tetraphenylphosphonium, crystal structures could be determined by X-ray diffraction. Complexes containing the highly unstable primary nitrosamines as ligands are generally scarce; moreover, to our knowledge this is the first example of isolated primary nitrosamines coordinated to a metal center through the NO moiety.