Synthesis, structure and reactivity of aliphatic primary nitrosamines stabilized by coordination to [IrCl5]2–

F. DI SALVO; D. A. ESTRIN; G. LEITUS; F. DOCTOROVICH

ORGANOMETALLICS

American Chemical Society

Lugar: Columbus, OH; Año: 2008 vol. 27 p. 1985 - 1995

0276-7333

  In the present work the formation of several primary aliphatic coordinated nitrosamines by reaction ofthe extremely reactive K[IrCl5(NO)] in acetonitrile solution with the corresponding amine is described.Complete characterization, including X-ray diffraction determinations for some examples, are reported,and experimental evidence of their stability. Density functional theory calculations (DFT) helped tounderstand the role of the coordination environment of these complexes and to support, with excellentcorrelation with the experimental data, the proposed reaction pathways and stability studies. Complexescontaining the highly unstable primary nitrosamines as ligands are generally scarce, and moreover, toour knowledge, our group has recently reported the first examples of isolated primary nitrosaminescoordinated to the metal center only through the NO moiety.