Electrophilic behavior of coordinated nitric oxide

The chemical mechanism of microbioal denitrification

“…This reaction has been demonstrated to occur with nitrosyls of Fe, Ru, and OS for a variety of nitrogenous nucleophiles [38], but not to our knowledge for nitrite. It should be noted that the ferrous porphyrin-nitrosyl complexes appear to be especially powerful nitrosylating agents…”

“…(ii) Nucleophilic attack on coordinatedNO has ample precedent [38], particularly when the bound NO has substantial positive character and a high N-O stretching frequency (e.g., reaction (5)). This reaction has been demonstrated to occur with nitrosyls of Fe, Ru, and OS for a variety of nitrogenous nucleophiles [38], but not to our knowledge for nitrite.…”

The nature of Ru–NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes—a computational study

“…Such complexes display a nitrosonium character of coordinated NO as observed in [RuNO(NH 3 ) 5 ] 3+ and in aqueous solution they may undergo nucleophilic attack for species such as OH − despite their stability. 37,42,43 The nitrosonium character of coordinated NO in trans-[Ru(NO)L(NH 3 ) 4 ] q+ complexes depends on ligand L trans to NO and the presence of macrocycle decreases the electrophilicity of coordinated NO compared to analogous complexes. 37 Although ruthenium nitrosyl amines are robust, the use of saturated macrocyclic polyamines as ligands restricts reactions to the ligands on the axial positions.…”

Structure of disodium nitronitrosylbis[2,4,5,6-(1H,3H)-pyrimidinetetrone 5-oximato(2–)]ruthenate(II) heptahydrate, Na2[Ru(C4HN3O4)2(NO)(NO2)].7H2O

“…Ketone oximato ligands are known to stabilize Ru complexes (Br6mard, Muller, Nowogrocki & Sueur, 1977). These nitrosyl complexes undergo nucleophilic attack at the nitrosyl group (Br~mard, Nowogrocki & Sueur, 1979), as for metal-nitrosyl complexes with a sufficiently high degree of NO+-like ligand character (Schfig & Guengerich, 1979;Walsh, Bullock & Meyer, 1980;Bottomley, 1978a). No X-ray structure of a ketone oximato nitrosyl complex has been reported.…”