Nitrosyl reaction with carbon monoxide

Carmona et al. (899) prepared another monomeric molybdenum(I) nitrosyl complex, mer-[Mo(NO)(PMe3)3(S2CNMe2)], from [MoCl(NO)(PMe3)4]. Further reaction with carbon monoxide yields frani-[Mo(NO)(CO)(S2CNMe2)(PMe3)2] via replacement of the phosphine trans to a molybdenum-sulfur bond (Eq. 78). 

Fig. 24. Proposed mechanism for the nitrosyl-catalyzed reaction of nitric oxide with carbon monoxide.

The reaction of nitrite complexes with carbon monoxide to yield the metal nitrosyl complex and carbon dioxide has been known for a consider-... 

Nitrosyls.— Treatment of the nitrosyl complex [Ir(NO)2(PPh3)2] lPFe] with carbon monoxide results in the formation of COg and NjO and [Ir(CO)3(PPh8)a] [PF6l The initial step in this reaction is believed to involve the coupling of two NO ligands to generate the intermediate The overall sequence shown in Scheme 2 is proposed. 

Hydroxyurea reacts with oxy, deoxy and metHb in vitro to form iron nitrosyl hemoglobin (HbNO) and transfers NO to 2-6% of the iron heme groups [115]. Trapping studies using cyanide and carbon monoxide indicate that hydroxyurea oxidizes both oxy and deoxyHb to metHb and reduces metHb to deoxyHb specifically identifying the reaction of hydroxyurea and metHb as the critical reaction in the formation of HbNO from hydroxyurea [115]. Scheme 7.16 depicts the proposed mechanisms of N O and HbNO formation during the reaction of deoxy and metHb with hydroxyurea. Oxidation of hydroxyurea by metHb produces deoxyHb and the nitroxide radical (25,... 

Formation of Ni(CO)4 or Co(CO)4- by the cyanide method depends upon the stepwise substitution of the anion of the cyano complex by the iso-electronic carbon monoxide molecule. By treating Co2(CO)8 with potassium cyanide we obtained cyanocarbonyls of cobalt of low oxidation number (83). In reactions of the nitrosyl carbonyls of iron and cobalt, Behrens (86) substituted all the CO groups with CN to give K3[Co(NO)(CN)3] or... 

The reaction is carried out in a 250-ml. three-necked flask which is swept out with dry, oxygen-free nitrogen. The metal carbonyl (5 g.) and degassed dichloromethane (50 ml.) are introduced. A solution of freshly distilled nitrosyl chloride (5 ml.) in dichloromethane is added dropwise and the reaction mixture stirred vigorously at 20°C. As the reaction takes place, carbon monoxide is evolved, and a green solid is produced. After stirring for 2 hours, the solvent is removed under vacuum and any unreacted carbonyl sublimed into a trap at — 196°C. The pure compound is obtained as a green powder. 

The reaction is conducted in an atmosphere of dry nitrogen, and the acetonitrile must be dried before use (molecular sieves are satisfactory), since nitrosyl hexafluorophosphate is easily hydrolyzed. To 2 g. of tricarbonyl- -cyclopentadienylmanganese1 in 100 ml. of acetonitrile is added dropwise, and with rapid stirring, a solution of 1.9 g. [NO] [PF6] in 30 ml. of acetonitrile. Carbon monoxide is evolved, and the solution becomes darker yellow. After the addition of the [NO][PF6] solution is complete (5 minutes), stirring is continued for 10 minutes to ensure complete reaction. The volume of the solvent is reduced to approximately 20 ml. by evaporation,... 

TIN, TIN FLAKE, or TIN POWDER (7440-31-5) Finely divided material is combustible and forms explosive mixture with air. Contact with moisture in air forms tin dioxide. Violent reaction with strong acids, strong oxidizers, ammonium perchlorate, ammonium nitrate, bis-o-azido benzoyl peroxide, bromates, bromine, bromine pentafluoride, bromine trifluoride, bromine azide, cadmium, carbon tetrachloride, chlorine, chlorine monofluoride, chlorine nitrate, chlorine pentafluoride, chlorites, copper(II) nitrate, fluorine, hydriodic acid, dimethylarsinic acid, nitrosyl fluoride, oxygen difluoride, perchlorates, perchloroeth-ylene, potassium dioxide, phosphorus pentoxide, sulfur, sulfur dichloride. Reacts with alkalis, forming flammable hydrogen gas. Incompatible with arsenic compounds, azochlo-ramide, benzene diazonium-4-sulfonate, benzyl chloride, chloric acid, cobalt chloride, copper oxide, 3,3 -dichloro-4,4 -diaminodiphenylmethane, hexafluorobenzene, hydrazinium nitrate, glicidol, iodine heptafluoride, iodine monochloride, iodine pentafluoride, lead monoxide, mercuric oxide, nitryl fluoride, peroxyformic acid, phosphorus, phosphorus trichloride, tellurium, turpentine, sodium acetylide, sodium peroxide, titanium dioxide. Contact with acetaldehyde may cause polymerization. May form explosive compounds with hexachloroethane, pentachloroethane, picric acid, potassium iodate, potassium peroxide, 2,4,6-trinitrobenzene-l,3,5-triol. 

Phosgene is used in the synthesis of dyes, pharmaceuticals, isocyanates, and pesticides and as a war gas. Exposure risk to this gas may arise when many common solvents, such as carbon tetrachloride, chloroform, or methylene chloride, are intensely heated. Photodecomposition of these solvents in air or oxygen can also generate phosgene in small amounts. It is also formed by the reaction of carbon tetrachloride with oleum, or of carbon monoxide with chlorine or nitrosyl chloride. 

Wang X, Zhou M, Andrews L (2000) Reactions of iron atoms with nitric oxide and carbon monoxide in excess argon infrared spectra and density functional calculations of iron carbonyl nitrosyl complexes. J Phys Chem A 104 10104-10111... 

Reaction of the nitrosylcarbonyl complex, [Mo(CO)2NOCp], with PPha results in the formation of [Mo(NCO)(CO)(PPha)2Cp], along with other reaction products. 56 The reaction pathway involves deoxygenation of the nitrosyl ligand and generation, from the nitrosyl, of an organometallic nitrene which then captures carbon monoxide to form isocyanate. 

---