Metal carbonyls sodium hydroxide, reaction with

HIDROXILAMINA (Spanish) (7803-49-8) A powerful reducing agent. Aqueous solution is a base. Contact with water or steam causes decomposition to ammonium hydroxide, nitrogen, and hydrogen. Contaminants and/or elevated temperatures above (reported at 158°F/70°C and 265°F/129°C) can cause explosive decomposition. Moisture in air or carbon dioxide may cause decomposition. Violent reaction with oxidizers, strong acids, copper(II) sulfate, chromium trioxide, potassium dichromate, phosphorus chlorides, metals calcium, sodium, zinc. Incompatible with carbonyls, pyridine. Forms heat-sensitive explosive mixtures with calcium, zinc powder, and possibly other finely divided metals. Aqueous solution incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, carbonyls, cellulose nitrate, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, glycols, isocyanates, ketones, nitrates, phenols, pyridine, vinyl acetate. Attacks aluminum, copper, tin, and zinc. 

The phase-transfer catalysed reaction of nickel tetracarbonyl with sodium hydroxide under carbon monoxide produces the nickel carbonyl dianions, Ni,(CO) 2- and Ni6(CO)162, which convert allyl chloride into a mixture of but-3-enoic and but-2-enoic acids [18]. However, in view of the high toxicity of the volatile nickel tetracarbonyl, the use of the nickel cyanide as a precursor for the carbonyl complexes is preferred. Pretreatment of the cyanide with carbon monoxide under basic conditions is thought to produce the tricarbonylnickel cyanide anion [19], as the active metal catalyst. Reaction with allyl halides, in a manner analogous to that outlined for the preparation of the arylacetic acids, produces the butenoic acids (Table 8.7). 

The carbonylchloroiridium(III) porphyrins can be transformed into a variety of other carbonyl complexes by chloride exchange with acids or salts (path e). Concentrated sodium hydroxide in ethanol appears to destroy the carbonyl ligand in these compounds (path — d, a) in a manner similar to the alkoxide addition to RhCl(TPP) CO (path f) here, this should give a carboxylic acid RhCOOH(P) which is decarboxylated to a hydride RhH(P) according to the typical base reaction of metal carbonyls. The hydride may then be autoxidized to the hydroxide. 

The first experiments which were carried out in the author s laboratory on organometallic phase-transfer catalysis were concerned with the reduction of nitrobenzenes (4) to anilines (5) by triiron dodecacarbonyl. Such a conversion was reported to occur in benzene containing methanol at reflux for 10-17 h, with the hydridoundecacarbonyltriferrate anion as the likely key intermediate (16). It was our expectation that the trinuclear iron hydride should be generated by phase-transfer catalysis and if so, effect reduction of nitro compounds (4) under exceedingly mild conditions. Indeed this was the case, as illustrated by the results shown in Table I (17). Not only is the reaction complete in 2 h or less using sodium hydroxide as the aqueous phase, benzene as the organic phase, and benzyltrieth-ylammonium chloride as the phase-transfer catalyst, but it occurs at room temperature and requires less metal carbonyl than when the reaction was... 

Phase-transfer catalysis can effectively promote the substitution of group 6 metal carbonyls by nitrogen, phosphorus, and arsenic ligands. Reaction of M(CO) [M = Cr, Mo, W] with a group 5 ligand and tetra-n-butylammonium iodide in benzene-sodium hydroxide (50%), at 25-80°C... 

The carbonylation of a benzyl halide in the presence of iron pentacarbonyl to give a phenylacetic acid may serve to exemplify the interaction of a metal carbonyl, carbon monoxide, PT catalyst, aqueous sodium hydroxide, and the substrate [79]. Fe(CO)5 is attacked by QOH at the interphase, and the species formed is extracted into the depths of the oganic phase, where it reacts with CO and benzyl halide (Eqs. 13 and 14). This new anion 3 is the actual catalyst. It reacts with a second benzyl halide to give a non-ionic intermediate 4 (Eq. 15). By insertion of CO and attack of QOH, 4 is decomposed to the reaction product under regeneration of 3 (Eq. 16). Thus, the action of the PT catalyst is twofold. Firstly it transports the metal carbonyl anion. More important seems to be its involvement in the (rate-determining) decomposition step. A basically similar mechanism was proposed for cobalt carbonyl reactions [80], which have been modified somewhat quite recently (see below). 

French) or BROMOFORMO (Spanish) (75-25-2) CHBrj Noncombustible liquid. Violent reaction with chemically active metals, acetone, calcium, strong caustics, potassium, potassium hydroxide, sodium hydroxide. Increases the explosive sensitivity of nitromethane. Incompatible with crown polyethers, sodium-potassium alloys. Forms friction- and shock-sensitive compounds with lithium. Aqueous solution is a medium-strong acid. Liquid attacks some plastics, rubber, and coatings. Corrosive to most metals in the presence of moisture. Thermal decon osition products include highly toxic carbonyl bromide and hydrogen bromide fumes. On small fires, use dry chemical powder (such as Purple-K-Powder), foam, or COj extinguishers. 

Reactions of fiuoroalkynes continue to attract considerable attention. A new route to (3,3,3-trifluoropropyne)hexacarbonyldicobalt involves the initial preparation of (3,3,3-trifluoro-l-trimethylsilylpropyne)hexacarbonyl-dicobalt in order to avoid the side reactions often encountered in the reactions of trifluoropropyne with metal carbonyls the trimethylsilyl group is finally removed by the action of methanolic sodium hydroxide ... 

The reaction of sodium hydroxide with metal carbonyls results in a nucleophilic attack by a hydroxide ion on the carbonyl group to give a... 

The reaction of sodium hydroxide with iron pentacarbonyl results in a nucleophilic attack by a hydroxide ion on the carbonyl group to give a metal carboxyHc add complex. Upon further action with sodium hydroxide, the carboxyHc add gives up carbon dioxide to form a hydrido anion. The protonation of this anion results in the formation of iron tet-racarbonyl hydride (Fleiber base) as... 

In the general context of donor/acceptor formulation, the carbonyl derivatives (especially ketones) are utilized as electron acceptors in a wide variety of reactions such as additions with Grignard reagents, alkyl metals, enolates (aldol condensation), hydroxide (Cannizzaro reaction), alkoxides (Meerwein-Pondorff-Verley reduction), thiolates, phenolates, etc. reduction to alcohols with lithium aluminum hydride, sodium borohydride, trialkyltin hydrides, etc. and cyloadditions with electron-rich olefins (Paterno-Buchi reaction), acetylenes, and dienes.46... 

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