Nitrosyl and Nitrogenyl Compounds

Aresta, P. Giannoccare, M. Rossi, and A. Sacco, Inorg. Chim. Acta, 1971, 5, 203. 

Jezowska-Trzebiatowska, P. Sobota, H. Kozlowski, and A. Jezierski, Bull. Acad, polon. Sci., 

Methods of preparation of the Fe nitroprussides, Fe2 Fe(CN)5NO 3,-9H2O and Fe Fe(CN)5NO Cl,0.5H2O have been described.Examination of the physical and chemical properties of [Fe(CN)5NO] shows the anion to formally contain Fe and should be formulated as Fe —NO not Fe — + ggj3 suggested that a blue species, formed when nitro- 

These reactions are followed by oxidation of [(NQjFefNCS)] by nitrous acid to [(NC)5Fe (NCS)]3-. 

Exposure of anhydrous sodium nitroprusside to y-rays at 77 K gave an e.s.r. spectrum consistent with [Fe fCNlgNO] and NO the reaction mechanism  

Nitrogenyl and Nitrosyl Compounds. There has been a suggestion that, in the reductive degradation of various cobalt(in) complexes, ammonia is evolved (when nitrogen-containing ligands are present) which is formed by fixation of N2. Detailed studies on [Co (tpps)] [tpps = meso-tetra-(p-sulphonatophenyl)- 

Cobaltocene reacts with dry oxygen in ether at — 78 °C to form (70), which is unstable in air. Treatment of this compound with phosphoric acid yields HjOj and [(Cp)2Co][H2P04], and reaction with PhCOCl gives dibenzoyl peroxide and (Cp)2CoCl. This is the first example of a transition-metal coordinated to an organic peroxide.  

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Nitrogenyl and Nitrosyl Compounds.—[FeH2(N2)(PEtPh2)3] reacts with ethylene (1 atm) in benzene, toluene, or THF. The product was not isolated, but spectral measurements in solution indicated that it can be formulated as [FeH(Et)(PEtPh2)2L] (L = PEtPh2 or solvent). The mechanism suggested for its formation is outlined below. 

Carbonyl, Nitrosyl, and Nitrogenyl Compounds.—[(Tt-Cp)NiLX] (L = PPhj, PPh2Me, PPhMc2, or PMCj X = Cl or Br) reacts with Na[Fe(CO)2(7r-Cp)] to form (114), which on treatment with stannous chloride gives (115). - ... 

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