Nickel complexes cyanides

Metal salts in alkaline solution Cuprammonium complex Nickel and cobalt ammonia complex Cyanides (q.v.) Copper pyrophosphates Plumbites Zincates... 

In addition to the tetrahedral and octahedral complexes mentioned above, there are two other types commonly found—the square planar and the linear. In the square planar complexes, the central atom has four near neighbors at the corners of a square. The coordination number is 4, the same number as in the tetrahedral complexes. An example of a square planar complex is the complex nickel cyanide anion, Ni(CN)4-2. 

Cyanides, including metal-cyanide complexes Drug residues Chromium, cadmium, lead, mercury, nickel. dissolve material used in sealing a site... 

Cyanide occurs most commonly as hydrogen cyanide in water, although it can also occur as the cyanide ion, alkali and alkaline earth metal cyanides (potassium cyanide, sodium cyanide, calcium cyanide), relatively stable metallocyanide complexes (ferricyanide complex [Fe(CN)6]-3), moderately stable metallocyanide complexes (complex nickel and copper cyanide), or easily decomposable metallocyanide complexes (zinc cyanide [Zn(CN)2], cadmium cyanide [Cd(CN)2]). Hydrogen cyanide and cyanide ion combined are commonly termed free cyanide. The environmental fate of these cyanide compounds varies widely (Callahan et al. 1979). 

Isomerism of the but-3-enoic acids into the E-but-2-enoic acids is base-catalysed (Table 8.8), whereas the formation of the other isomers indicates the participation of rt-allylnickel complexes in the reaction. Potassium nickel tetracarbonyl is a considerably poorer catalyst, compared with nickel cyanide, whereas nickel sulphate and nickel iodide are ineffective catalysts. 

Additive or more-than-additive toxicity of free cyanide to aquatic fauna has been reported in combination with ammonia (Smith et al. 1979 Leduc et al. 1982 Alabaster et al. 1983 Leduc 1984) or arsenic (Leduc 1984). However, conflicting reports on the toxicity of mixtures of HCN with zinc or chromium (Towill et al. 1978 Smith et al. 1979 Leduc et al. 1982 Leduc 1984) require clarification. Formation of the nickelocyanide complex markedly reduces the toxicity of both cyanide and nickel at high concentrations in alkaline pH. At lower concentrations and acidic pH, solutions increase in toxicity by more than 1000-fold, owing to dissociation of the metallo-cyanide complex to form hydrogen cyanide (Towill et al. 1978). Mixtures of cyanide and ammonia may interfere with seaward migration of Atlantic salmon smolts under conditions of low dissolved oxygen (Alabaster et al. 1983). The 96-h toxicity of mixtures of sodium cyanide and nickel sulfate to fathead minnows is influenced by water alkalinity and pH. Toxicity decreased with increasing alkalinity and pH from 0.42 mg CN/L at 5 mg CaCOj/L and pH 6.5, to 1.4 mg CN/L at 70 mg CaCOj/L and pH 7.5 to 730 mg CN/L at 192 mg CaCOj/L and pH 8.0 (Doudoroff 1956). 

Otherwise, unusual valency states are often observed in cyanide complexes. A Mn complex K5Mn(CN)6 has been reported here the stable 18-electron configuration causes the valency of manganese to take the very unusual value of one, and the compound is formed in spite of the extremely unfavourable cation anion ratio. Still more remarkable are the complex nickel cyanides. KGN and Ni(CN)2 form a complex K2Ni(CN)4, in which sixteen electrons are involved in the bond formation. The diamagnetism and the square structure of the Ni(CN)4 ion show that the bonding is due to dsp2 hybridization. 

Because of its low acidity, hydrogen cyanide seldom adds to nonactivated multiple bonds. Catalytic processes, however, may be applied to achieve such additions. Metal catalysts, mainly nickel and palladium complexes, and [Co(CO)4]2 are used to catalyze the addition of HCN to alkenes known as hydrocyanation.l67 l74 Most studies usually apply nickel triarylphosphites with a Lewis acid promoter. The mechanism involves the insertion of the alkene into the Ni—H bond of a hydrido nickel cyanide complex to form a cr-alkylnickel complex173-176 (Scheme 6.3). The addition of DCN to deuterium-labeled compound 17 was shown to take place... 

A number of review articles covering aspects of cobalt, nickel, or copper chemistry have appeared. These include metal cyanide complexes of phosphines,916 higher... 

Very recently Geus and co-workers [44, 45] have applied another method based on chemical complexes. This is the complex cyanide method to prepare both monocomponent (Fe or Co) and multicomponent Fischer-Tropsch catalysts. A large range of insoluble complex cyanides are known in which many metals can be combined, e.g. iron(n) hexacyanide and iron(m) hexacyanide can be combined with iron ions, but also with nickel, cobalt, copper, and zinc ions. Soluble complex ions of molybdenum(iv) which can produce insoluble complexes with metal cations are also known. Deposition precipitation (Section A.2.2.1.5) can be performed by injection of a solution of a soluble cyanide complex of one of the desired metals into a suspension of a suitable support in a solution of a simple salt of the other desired metal. By adjusting the cation composition of the simple salt solution, with a same cyanide, it is possible to adjust the composition of the precursor from a monometallic oxide (the case when the metallic cation is identical to that contained in the complex) to oxides containing one or several foreign elements. 

Powell HM, Rayner JH (1949) Clathrate compound formed by benzene with an ammonia-nickel cyanide complex. Nature 163 566-567... 

A drawback connected with the tendency of Ni(0) to undergo oxidative addition of HCN is the formation of inactive nickel cyanide complexes. Such inhibition can be overcome, however, by keeping the HCN concentration low. This also has the further advantage of preventing sudden temperature increases arising from the high exothermicity of the reactions with HCN. 

Asynunetric Synthesis by Homogeneous Catalysis Cyanide Complexes of the Transition Metals Electronic Stmcture of Organometalhc Compounds Hydride Complexes of the Transition Metals Mechanisms of Reaction of Organometalhc Complexes Nickel Organometalhc Chemistry P-donor Ligands. 

Table 4. Selected IR properties of some carbonyl and cyanide complexes of nickel and iron with the PS3 and PS3 ligands [70, 71).

It is often found to be beneficial to carry out electrodeposition from solutions that contain metal ions in the form of a complex rather than the aquated metal ion. A striking example is silver, which forms large, loose crystals when deposited from silver nitrate, but a smooth, adherent, white layer when deposited from a cyanide bath. Nickel cannot be deposited at all from strongly acidic solutions, whereas quantitative deposition can be achieved from ammoniacal solutions. 

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