HNO (nitroxyl, azanone), joined the ‘biologically relevant reactive nitrogen species’ family in the 2000s.

Synthesis of a pincer-type linear nitrosyl complex [Rh(P^tBu₂CN^Et₂)(NO)]⁺ (3⁺) is described. The product and all intermediates involved were fully characterized by FTIR, NMR, cyclic voltammetry and X-ray crystallography. Attempts at obtaining (3⁺) from its chlorinated precursor Rh(PCN)(NO)Cl (2) revealed that a relative stabilization of this complex ion is introduced by the BArF⁻ counteranion, as other counteranions—PF₆ ⁻, BF₄ ⁻ and triflate—proved to coordinate to the metal center. Redox reactivity both of (3⁺) and of that of its five-coordinate derivatives (2) and [Rh(PCN)(NO)(CH₃CN)]⁺ (4⁺) was found to distinguish itself from analogous PCP complexes due to a relative stabilization of higher oxidation states. Oxidation of these three complexes was studied by FTIR spectroelectrochemistry. Reduction of complex (3⁺) to yield a short-lived {RhNO}⁹ species [Rh(PCN)(NO)]˙ (3˙) was also carried out. Complex (3˙) was proved able to activate carbon–halogen bonds in aryl halides, in much a similar way as that of its PCP analogue. Complex (3⁺) was also seen to establish a linear ↔ bent nitrosyl equilibrium upon addition of CO which could not be fully displaced with excess CO.

NO˙ disproportionation by the pincer-type complex [Rh(PCP^tBu)(NO)]˙ (1˙) results in the formation of Rh(PCP^tBu)(NO)(NO₂) (2) with coordinated nitrite and quantitative release of N₂O.

In the past decade, gasotransmitters NO^• and H₂S have been thoroughly studied in biological contexts, as their biosynthesis and physiological effects became known. Moreover, an additional intricate crosstalk reaction scheme between these compounds and related species is thought to exist as part of the cascade signaling processes in physiological conditions. In this context, heme enzymes, as modeled by iron porphyrins, play a central role in catalyzing the key interconversions involved. In this work, iron porphyrin interactions with sulfide and nitric-oxide-related species are described. The stability and reactivity of mixed ternary systems are also described, and future perspectives are discussed.