Chapter 7. Non-heme HNO Complexes

OLABE, JOSÉ A.; BARI, SARA E.; SLEP, LEONARDO D.

The Chemistry and Biology of Nitroxyl (HNO)

Elsevier

Año: 2016; p. 127 - 154

The coordination chemistry of nitroxyl (HNO) withtransition metals is described comprising synthetic aspects, structure andreactivity in different modes. HNO is an intermediate in the redoxtransformations of nitrite to ammonia, and the studies with non-heme systems allowunderstanding its chemical and biologically relevant properties. Pseudo-octahedralHNO complexes affording low-spin d6 configurations [ML5(NHO)]n(M = Mo, Re, Fe, Ru, Os, Co, Rh, Ir) with ancillary L coligands were preparedin aqueous and non aqueous media through reduction or oxidation of adequate nitrosylor nitrogen-hydride precursors. X-ray structures for isolated compounds,diverse spectroscopies (NMR, IR, UV-vis, etc) in solid state and solution,electrochemistry, theoretical calculations and kinetic/mechanistic methodologieswere used for describing the bonding, stability and reactivity properties likethe formation/dissociation reactions from the metals, acid-base propertiesgenerating the NO− anion, and redox reactions of both the HNO/NO−bound species.