Nickel Nonaqueous

Electroplated Metals and Alloys. The metals electroplated on a commercial scale from specially formulated aqueous solutions iaclude cadmium, chromium, cobalt, copper, gold, iadium, iron, lead, nickel, platinum-group metals, silver, tin, and ziac. Although it is possible to electroplate some metals, such as aluminum, from nonaqueous solutions as well as some from molten salt baths, these processes appear to have achieved Httie commercial significance. 

For mixed lanthanide-transition metal clusters, Yukawa et al. have synthesized an octahedral [SmNi6] cluster by the reaction of Sm3+ and [Ni(pro)2] in nonaque-ous medium [66-68]. The six [Ni(pro)2] ligands use 12 carboxylate oxygen atoms to coordinate to the Sm3+ ion, which is located at the center of an octahedral cage formed by six nickel atoms. The coordination polyhedron of the central Sm3+ ion may be best described as an icosahedron. The [SmNir, core is stable in solution but the crystal is unstable in air. The cyclic voltammogram shows one reduction step from Sm3+ to Sm2+ and six oxidation steps due to the Ni2+ ions. Later, similar [LaNis] and CjdNif> clusters were also prepared. 

As we have seen, an area of major importance and of considerable interest is that of substitution reactions of metal complexes in aqueous, nonaqueous and organized assemblies (particularly micellar systems). The accumulation of a great deal of data on substitution in nickel(II) and cobalt(II) in solution (9) has failed to shake the dissociative mechanism for substitution and for these the statement "The mechanisms of formation reactions of solvated metal cations have also been settled, the majority taking place by the Eigen-Wilkins interchange mechanism or by understandable variants of it" (10) seems appropriate. Required, however, are more data for substitution in the other... 

Water is a possible axial ligand for the transient Ni(PP) in these systems and has been shown to form weak complexes with other nickel porphyrin species (18). While we cannot unequivocally rule out weak, transient ligation, the observation of similar transient behavior in Ni(OEP) and Ni(PPDME) in noncoordinating, nonaqueous, solvents (toluene, methylene chloride (9, unpublished results)) leads us to conclude that the transient behavior of the Ni(PP) in acetone/water is not predicated upon ligand binding. 

Nonactive/slightly reactive electrode materials include metals whose reactivity toward the solution components is much lower compared with active metals, and thus there are no spontaneous reactions between them and the solution species. On the other hand, they are not noble, and hence their anodic dissolution may be the positive limit of the electrochemical windows of many nonaqueous solutions. Typical examples are mercury, silver, nickel, copper, etc. It is possible to add to this list both aluminum and iron, which by themselves may react spontaneously with nonaqueous solvent molecules or salt anions containing atoms of high oxidation states. However, they are not reactive due to passivation of the metal which, indeed, results from the formation of stable, thin anodic films that protect the metal at a wide range of potentials, and thus the electrochemical window is determined by the electroreactions of the solution components [51,52],... 

A nonactive electrode may include noble metals such as gold, silver, and platinum, the so-called sp-metals such as In, Ga, Cd, Bi, as well as transition (or d) metals such as nickel or cobalt. Carbon electrodes and semiconductors such as indium tin oxide [1], diamond [2], and conducting polymers may fall into the category of nonactive electrodes in appropriate solutions, as do composite materials that contain metal oxides or chalcogenides. The behavior of active electrodes in nonaqueous solution is discussed separately in the next chapter. 

Up until now, there has been little interest in electrolytic deposition of iron metals and chromium from nonaqueous solutions, because such deposits are easily obtained from aqueous electrolytes. On the other hand, adhesive layers can be applied to reactive metals like titanium, beryllium, and magnesium, for example through nickel deposition from nonaqueous solutions. By depositing such metals out of nonaqueous solutions, hydrogen sensitive materials, such as low-alloy high-strength steel, can be coated without danger of embrittlement. Materials coated in this way with a compact poreless metal layer can be further coated in an aqueous electrolyte. 

The solvent properties of alcohols with short carbon chains are similar to those of water and such alcohols could be used as the nonaqueous catalyst phase when the products are apolar in nature. The first commercial biphasic process, the Shell Higher Olefin Process (SHOP) developed by Keim et al. [4], is nonaqueous and uses butanediol as the catalyst phase and a nickel catalyst modified with a diol-soluble phosphine, R2PCH2COOH. While ethylene is highly soluble in butanediol, the higher olefins phase-separate from the catalyst phase (cf. Section 2.3.1.3). The dimerization of butadiene to 1,3,7-octatriene was studied using triphenylphosphine-modified palladium catalyst in acetonitrile/hexafluoro-2-phe-nyl-2-propanol solvent mixtures [5]. The reaction of butadiene with phthalic acid to give octyl phthalate can be catalyzed by a nonaqueous catalyst formed in-situ from Pd(acac)2 (acac, acetylacetonate) and P(0CeH40CH3)3 in dimethyl sulfoxide (DMSO). In both systems the products are extracted from the catalyst phase by isooctane, which is separated from the final products by distillation [5]. 

The addition of HCN to C=C double bonds can be effected in low yields to produce Markovnikov addition products. However, through the use of transition metal catalysts, the selective anti-Markovnikov addition of HCN to alkenes can take place. The most prominent example of the use of aqueous media for transition metal-catalyzed alkene hydrocyanation chemistry is the three-step synthesis of adi-ponitrile from butadiene and HCN (Eqs. 5-7). First discovered by Drinkard at DuPont [14], this nickel-catalyzed chemistry can use a wide variety of phosphorus ligands [15] and is practiced commercially in nonaqueous media by both DuPont and Butachimie, A DuPont/Rhone-Poulenc joint venture. Since the initial reports of Drinkard, first Kuntz [16] and, more recently, Huser and Perron [17, 18] from Rhone-Poulenc have explored the use of water-soluble ligands for this process to facilitate catalyst recovery and recycle from these high-boiling organic products. 

With nonaqueous media, apparatus constructed of iron and lined with plastics, such as Teflon, Kel-F, Saran, polyvinyl chloride, polyesters, epoxy resins, or with stoneware, enamel, porcelain, glass, lead, nickel, Inconel, stainless steel, Hastelloy, Duriron, glazed tile, carbon brick, Karbate, titanium, tantalum, and zirconium can be used for the whole plant or specific apparatus. 

The initial tests of the sodium dispersion-metal halide system were made with ferric chloride, fortunately, and with a nonaqueous solvent in which ferric chloride was soluble. Thus, ferric chloride was present as a solution and, consequently, presented maximum surface for contact with the sodium particles. This feature, coupled with the lower activation energy requirements, permitted the reaction to proceed at temperatures well below room temperature and established the operability of the method. The success of the initial (ferric chloride) tests lent encouragement to tests on other metal systems and prompted continued investigations when the initial runs at lower temperatures failed. The discovery of the threshold, or trigger, temperature for nickel (II) chloride reduction paved the way for successful reduction of other metal halides such as manganese (II) chloride, cobalt (II) chloride, and cadmium bromide. 

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