Cyanides, metal, reaction with

Complexation constants of crown ethers and cryptands for alkali metal salts depend on the cavity sizes of the macrocycles 152,153). ln phase transfer nucleophilic reactions catalyzed by polymer-supported crown ethers and cryptands, rates may vary with the alkali cation. When a catalyst 41 with an 18-membered ring was used for Br-I exchange reactions, rates decreased with a change in salt from KI to Nal, whereas catalyst 40 bearing a 15-membered ring gave the opposite effect (Table 10)l49). A similar rate difference was observed for cyanide displacement reactions with polymer-supported cryptands in which the size of the cavity was varied 141). Polymer-supported phosphonium salt 4, as expected, gave no cation dependence of rates (Table 10). 

Hydroxyquinoline is a group reagent often applied to the precipitation or extraction of a large number of metals. The selectivity of metal reactions with oxine may be enhanced by masking agents such as EDTA, tartrate, oxalate, or cyanide. 

Using functionalized 3,4-dialkyl pyridines, Shiao and co-workers have described an alternative synthesis of actinidine (183) based on mixed metal reactions with l-(alkoxycarbonyl)pyridinium salts. Thus, ethyl 3-iodopropi-onate was successively treated with zinc and cuprous cyanide, and after being cooled to —78°C the resulting solution was reacted with 5-methyl-methylnicotinoate (158) and the mixture warmed to room temperature to afford 159. Cyclization and decarboxylation was effected with sodium hydride followed by heating in aqueous solution to afford 160. A Wittig reaction on 160 gave the olefin 161, and catalytic hydrogenation (Pd-C) afforded ( )-actinidine (134) (Scheme 5) (183). 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Many reactions can be carried out between potassium cyanide and organic compounds with the alkalinity of the KCN acting as a catalyst these reactions are analogous to reactions of sodium cyanide. The reactions of potassium cyanide with sulfur and sulfur compounds are also analogous to those of sodium cyanide. Potassium cyanide is reduced to potassium metal and carbon by heating it out of contact with air in the presence of powdered magnesium. Magnesium is converted to the nitride ... 

Beryllium, calcium, boron, and aluminum act in a similar manner. Malonic acid is made from monochloroacetic acid by reaction with potassium cyanide followed by hydrolysis. The acid and the intermediate cyanoacetic acid are used for the synthesis of polymethine dyes, synthetic caffeine, and for the manufacture of diethyl malonate, which is used in the synthesis of barbiturates. Most metals dissolve in aqueous potassium cyanide solutions in the presence of oxygen to form complex cyanides (see Coordination compounds). 

The basis for the toxicological activity of this substance is the reaction of cobalt ion with cyanide ion to form a relatively nontoxic and stable ion complex. The hexacyanocobaltate ion contains a Co2+ central metal ion with six cyanide ions as ligands. This coordination complex involves six coordinate covalent bonds whereby each cyanide ion supplies a pair of electrons to form each covalent bond with the central cobalt ion. The formation constant for the hexacyanocobaltate ion is even larger than for dicobalt EDTA,3 and thus the cobalt ion preferentially exchanges an EDTA ligand for six cyano ligands ... 

However, selenium and tellurium do not react with hydrogen, so the hydrogen compounds are prepared by reacting the elements with a metal, then treating it with an acid. Selenium and tellurium undergo addition reactions with cyanides to yield selenocyanates and tellurocyanates ... 

X. Wu, X. Li, F. King, J. Xiao, Angew. Chem. Int. Ed. 2005, 44, 3407. Surprisingly, no direct references to cyanide inhibition of hydrogenation catalysts could be found. For a general reaction showing the swift reaction of a transition metal complex with cyanide as a means to isolate the ligand, see for ex-... 

The ability of cyanide to form complexes with some metallic ions such as cobalt is the basis for the reaction with hydroxocobalamin that yields cyanocobalamin. Cyanocobalamin (vitamin B12), which contains cyanide and cobalt, is essential for the health of mammalian organisms. 

Cyanide s binding to metallic ions is also employed in a reaction with cobalt-containing compounds that yields cyanocobalamin (see Section 2.6). Cobalt compounds generally are not used because of their toxicity however, Co2EDTA (Klimmek et al. 1983) and hydroxocobalamin (Benabid et al. 1987 Mengel et al. 1989 Mushett et al. 1952) have been used as antidotes both in clinical and laboratory trials. Cardiac toxicity from Co2EDTA use under clinical conditions has raised caution in its clinical use, as the cardiac... 

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). 

Long-lived homogeneous Pd(0)f4 [L = P(Ph)3] catalysts for the cyanation of aryl chlorides (295) (X = Cl) have been developed, which are activated by cathodic reduction (Scheme 113) [433]. A high temperature, 130 °C, and a high-boihng solvent, dimethylformamide, are required because Pd does not insert into the aryl C—Cl bond at lower temperatures. Cat-alytically inactive metal species formed in undesirable side reactions with cyanide are electrochemically restored to a catalytically... 

Copper(i).—Halides and Cyanides.cation, [Me2N=CH2] , which has been reported previously by Eschenmoser (Symposium on Stereochemistry, Sheffield, 1970) is potentially useful in stabilizing low-valent metal complexes, and its reaction with Cu(CO)Cl has been examined. The results are outlined in Scheme 9. 

With organic acids, the reaction is slow. Reactions with sodium cyanide or potassium cyanide in aqueous solutions yield complex metal cyanide. For example, with potassium cyanide, the product is potassium tetracyanocad-mate ... 

Mdssbauer spectra of bonding and structure in, 15 184-187 reactions with diborane, 16 213 stabilization of, 5 17, 18-19 cyanates, 17 297, 298 cyanide complexes of, 8 143-144 cyclometallated bipyridine complex, 30 76 diazene complexes, 27 231-232 dinitrogen complexes, 27 215, 217 diphosphine complexes of, 14 208-219 dithiocarbamates, 23 253-254 -1,2-dithiolene complexes, 22 323-327 hydrogen bonding, 22 327 halide complexes with phosphine, etc., 6 25 hexaflouride, structure, 27 104 hydride complexes, 20 235, 248-281, see also Transition metal-hydride complexes... 

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