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

Abstract

In the present work we describe the formation of primary aromatic and aliphatic coordinated nitrosamines by reaction of the extremely reactive K[IrCl 5 -NO] 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.

Electronic Perturbation in a Molecular Nanowire of [IrCl5(NO)]− Units

“…À but with a different counterion, NaA C H T U N G T R E N N U N G [IrCl 5 (NO)], the anions are stacked one over the other in a sideby-side arrangement. In this case the electronic distribution can be depicted as the closed-shell electronic structure Ir III ÀNO + , as expected for any d 6 thirdrow transition metal complex.…”

“…In this case the electronic distribution can be depicted as the closed-shell electronic structure Ir III ÀNO + , as expected for any d 6 thirdrow transition metal complex. However, in PPh 4 A C H T U N G T R E N N U N G [IrCl 5 (NO)] an unprecedented electronic perturbation takes place, probably due to NOC-Cl À acceptordonor interactions among a large number of [IrCl 5 …”

“…This is probably induced by electrostatic interactions acting as a result of the closeness and wire-like spatial arrangement of the Ir metal centers, imposed by lattice forces due to p-p stacking interactions among the phenyl rings in PPh 4 + . Experimental and theoretical data indicate that in PPh 4 A C H T U N G T R E N N U N G [IrCl 5 (NO)] the Ir À N À O moiety is partially bent and tilted. Keywords: electron transfer · iridium · nanostructures · nitrosyl · valence isomerization markable reactivity [5,6] observed in solution.…”

“…Experimental and theoretical data indicate that in PPh 4 A C H T U N G T R E N N U N G [IrCl 5 (NO)] the Ir À N À O moiety is partially bent and tilted. Keywords: electron transfer · iridium · nanostructures · nitrosyl · valence isomerization markable reactivity [5,6] observed in solution. According to the formalism of Enemark and Feltham, [7] the crystal structure of this hexacoordinated {MNO} 6 comprises an octahedral anion with a practically linear IrÀNO moiety (Ir-N-O 174.38).…”

“…[1] The nitrosyl in KA C H T U N G T R E N N U N G [IrCl 5 (NO)] is probably the most electrophilic electron-poor nitrosyl ("NO + ") known to date. This fact is reflected by its extremely high IR frequency in the solid state (2006 cm À1 ), [2] electrochemical behavior, [3,4] and re-…”