Halides nitric oxide

Pentacarbonyliron Acetic acid, nitric oxide, transition metal halides, water, zinc... 

Nitric oxide is made commercially by oxidation of ammonia above 500°C in the presence of platinum, or by reduction of nitrous acid with ferrous sulphate or feiTous halides. The physical ... 

Metal carbonyls form several complexes but those of major interest in MOCVD are the carbonyl halides and the carbonyl-nitric-oxide complexes. 

It is possible to replace one isocyanide by triphenylphosphine, or to replace two isocyanides with diphos, giving phosphine analogues of these complexes. These species are not available from analogous reactions of phosphine-palladium(O) and (II) complexes. Reactions with active alkyl halides proceeds with oxidation nitric oxide also oxidizes these complexes. [Eqs. (31, 32)]. 

Palladium Paraformaldehyde Paraldehyde Pentaborane-9 Pentacarbonyliron Arsenic, carbon, ozonides, sulfur, sodium tetrahydridoborate Liquid oxygen Alkalies, HCN, iodides, nitric acid, oxidizers Dimethylsulfoxide Acetic acid, nitric oxide, transition metal halides, water, zinc... 

The diazeniumdiolate anions react with electrophiles to produce stable covalent compounds (Fig. 3.9) [213, 216]. These compounds have the ability to act as prodrugs, releasing nitric oxide only when metabolically or enzymatically converted to the diazeniumdiolate anion [217-219]. Several compounds ofthis class have been synthesized by reaction of alkyl or aryl halides, sulfate esters, epoxides, etc. with the ionic diazeniumdiolates [220, 221]. 

Silylated triphosphanes and triphosphides, synthesis, 31 188-194 yields, 31 194 Silylenes, 29 2-6 addition reactions, 29 4-6 to butadiene, 29 4 to ethylene, 29 4 to hexadienes, 29 5 mechanism, 29 4 nitric oxide scavenging, 29 4 complexes, 25 37, 51, 116, 118 as catalyst intermediates, 25 118 extrusion from disilanes, 25 114, 118 halides, 3 225 from hydridosilanes, 25 14 insertion into element-hydrogen bonds, 29 3-4... 

This solvent- and halide-free oxidation of cyclohexene and cyclopentene is clean, safe, and reproducible, with conditions that are less corrosive than those of the nitric acid oxidation. No operational problems are foreseen for a large-scale version of this green process, and technical refinement should further increase the synthetic effi-... 

Iron-centered paramagnetic complexes formed by reactions between iron salts and nitric oxide in the presence of anionic ligands, and characterized by g = 2.03, were first reported over 20 years ago (22) similar complexes, of the general type [Fe(NO)2X2] +, have subsequently been produced by reactions of iron salts and nitric oxide in the presence of halides and pseudohalides (118), alcohols and alkoxides (119), mercaptides (120, 121), and mercaptopurines and mercaptopy-rimidines (122). 

Cupric halides in alcohols absorb nitric oxide giving unstable blue or violet species. Decomposition leads to alkyl nitrites, presumably via RO- attack (equation 22). 

Fluorine Phosphorus halides Iodine chloride Phosphorus trichloride Lead(IV) oxide Non-metal halides Nitric acid Phosphorus halides Selenium dioxide Phosphorus trichloride Sodium peroxide Non-metal halides... 

Another case for which ET could be expected as a viable alternative to the SN2 displacement mechanism concerns the reactions of CH3I and CC14 with the nitric oxide anion, NO-263. Because of the extremely low electron affinity of NO (0.024- 0.55 kcalmof1), an ET process to the halo-compounds would be exothermic. However, in neither case was the substrate radical anion observed, despite the fact that both have bound molecular anions. Both reactions yield only the halide ion, a product which can arise via dissociative ET (a) or S 2 (b) (Scheme 38). The mechanism could not be assigned. 

A consequence of photolysis and of atom abstraction from atmospheric carbonyl halides is the production of haloformyl radicals, XCO. These may react (equation 63) with molecular oxygen to form haloformylperoxy radicals XC(0)02, which in turn may be reduced (equation 64) by nitric oxide to yield haloformyloxy radicals XC(0)0. 

Nitric Oxide Halide Complexes. The dimeric diamagnetic halides [Fe(NO)2X]2 have essentially tetrahedrally coordinated iron atoms with bridging halides. The trinitrosyl halides [Fe(NO)3X] are comparatively much less stable they can be prepared by the reaction of [Fe(CO)2X]2 with iron and nitric oxide. The complexes [Fe(NO)X3] and [Fe(NO)2X2] are known but much more work has been done on the reactivity of the dimeric dinitrosyl, and some of its reactions are illustrated in Scheme 2. 

Nitric oxide forms nitrosyl halides in the reaction with chlorine and bromine (see Section 9.1) in the reaction with fluorine, both nitrosyl fluoride and trifluoramine oxide are formed (see Section 9.3). 

Nitrosyl chloride can be obtained by direct combination of chlorine with nitric oxide, by the reaction of NOHSO4 or NaNOj with HCl, or as a by-product in the preparation of KNOs from KCl and NO2, in which KCl is moistened with 2.4% water. Nitrosyl bromide is usually prepared by direct combination of bromine nuth nitric oxide. Nitrosyl chloride and nitrosyl bromide can be prepared by reacting the appropriate potassium halide with nitrogen dioxide at room temperature. The reaction rate increases with increased size of the halide, and NOCl and NOBr can be obtained in a reasonable length of time by powdering the halide salt before adding NO. ... 

Reaction of nitric oxide with high oxidation state metal halides can lead to reduction to low-valent nitrosyl compounds, with elimination of nitrosyl halide. This route has been used particularly for early transition metal compounds and some examples from molybdenum chemis-... 

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