Nickel complexes Subject

Subjecting 2 or 3 to strongly acidic conditions (e.g. 1 M CF3CO2H or concentrated HQ) leads to rapid demetalation and the production of two isomeric free-base macrocycles 10 and 11 [11, 12]. The structure of 10 was conflrmed by its spectral properties and its remetalation to form the nickel complex 5. On the other hand, the structure of 11 was determined solely by its spectral properties. For instance, the NMR spectrum of 11 demonstrated the presence of a fully unsaturated system. Typical also was the presence of pyrrolic proton signals in the 6-7 ppm range of the NMR spectrum [12]. Compound 11 was very unstable... 

The exact nature of the complex from which the final reductive elimination occurs remains subject to speculation. The involvement of a five-coordinate nickel complex RNiLsCN-A appears likely, based on the observation that reductive elimination of benzonitrile from PhNi(Et3P)2(CN) is promoted by adding triethyl phosphite, and that reductive elimination of propionitrile from EtNi[P(0-o-tolyl)3](C2H4)(CN) is first order in triaryl phosphite concentration. ... 

The oligomerization of ethylene in the presence of nickel complexes with chelating P—P, P—0,0—0, and P—N ligands are the subject of a brief review. The asymmetric codimerization of ethylene and norbomene shown in equation... 

Coppens and coworkers reported the first experimental evidence for the presence of side-on nitrosyl bound isomer of any group 10 nitrosyl complex MNO ("65j. In their work, they collected X-ray diffraction data sets on a crystal of Cp Ni(NO) (Figure 20) and subjected the same crystal at 25 K to 485 nm light from an Ar laser for 3 h. Analysis of the diffiraction data before and after irradiation revealed the formation of a new species identified as the side-on // -NO bound nickel complex, accompanied by a shortening of the Ni—O distance, a shght shortening of the Ni—N distance, and a tightening of... 

Frontier with the subject of this paragraph, the use of early and late metal complexes combinations for reactor blending during ethylene polymerization can also be mentioned. In such a process, known since the 1980s, the early and late catalysts polymerize ethylene independently to afford an intimate mixture of polyethylene PE) chains of different structure. Although in this case there is no cooperative effect of the two metals from a molecular or mechanistic point of view, the beneficial simultaneous use of the two catalysts, such as a dichlorozirconocene and a diimine nickel complex (Scheme 58) ([147] and references therein), is found in the bulk physicochemical properties of the obtained PE. 

This contribution provides an overview of contemporary synthetic methods of broad applicability that involve the preparation and use of nickel jt-complexes as starting materials or reactive intermediates. Numerous excellent reviews on the chemistry of nickel have appeared that are complementary to this contribution in subject and scope. An outstanding review by Chetcuti describes the knovm jt-complexes of nickel,I l and several other structural classes of nickel complexes have been reviewed " o-bonded organo-nickel compounds are reviewed in Houben-Weyl, Vol. 13/9b, pp 632-700. The historical development and early applications of nickel chemistry have been reviewed byWilkePl and Jolly,I ] industrial applications have been reviewed by Keim,Pl and several other reviews on specific groups of synthetic transformations have appeared. The organometallic... 

The addition of HCN to olefins catalyzed by complexes of transition metals has been studied since about 1950. The first hydrocyanation by a homogeneous catalyst was reported by Arthur with cobalt carbonyl as catalyst. These reactions gave the branched nitrile as the predominant product. Nickel complexes of phosphites are more active catalysts for hydrocyanation, and these catalysts give the anti-Markovnikov product with terminal alkenes. The first nickel-catalyzed hydrocyanations were disclosed by Drinkard and by Brown and Rick. The development of this nickel-catalyzed chemistry into the commercially important addition to butadiene (Equation 16.3) was conducted at DuPont. Taylor and Swift referred to hydrocyanation of butadiene, and Drinkard exploited this chemistry for the synthesis of adiponitrile. The mechanism of ftiis process was pursued in depth by Tolman. As a result of this work, butadiene hydrocyanation was commercialized in 1971. The development of hydrocyanation is one of tfie early success stories in homogeneous catalysis. Significant improvements in catalysts have been made since that time, and many reviews have now been written on this subject. ... 

Allyl complexes have contributed significantly to the development of the organometallic chemistry of nickel and the applications of nickel complexes in organic synthesis, for example, nucleophilic attack on coordinated allyl ligands. In addition, allylnickel complexes have been identified as key intermediates in the oligomerization and cyclization of olefins and dienes. For example, the Ni(0)-catalyzed hydrocyanation of butadiene to adiponitrile, the main component of a major commercial process for the production of nylon, involves Ni (7r-allyl) intermediates. Moreover, the 77-rearrangements of allylnickel species have helped explain the facile isomerization of olefins in the presence of nickel complexes. The Ni-catalyzed homoallylation of carbonyl compounds with 1,3-dienes also involves Ni(7r-allyl) complexes this subject has been reviewed recently. New applications include the cleavage of G-G bonds in the deallylation of malonates, the preparation of cyclopentenones by carbonylative cycloaddi-... 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

The most widely used method for adding the elements of hydrogen to carbon-carbon double bonds is catalytic hydrogenation. Except for very sterically hindered alkenes, this reaction usually proceeds rapidly and cleanly. The most common catalysts are various forms of transition metals, particularly platinum, palladium, rhodium, ruthenium, and nickel. Both the metals as finely dispersed solids or adsorbed on inert supports such as carbon or alumina (heterogeneous catalysts) and certain soluble complexes of these metals (homogeneous catalysts) exhibit catalytic activity. Depending upon conditions and catalyst, other functional groups are also subject to reduction under these conditions. 

In practice, the defect structure of the materials LiJCo, M)02 and Lix(Ni, M)02 under oxidizing conditions found at cathodes, is complex. For example, oxidation of Fe3+ substituted lithium nickelate, LL(Ni, Fe)02, under cathodic conditions leads to the formation of Fe4+ and Ni4+. Conductivity can then take place by means of rapid charge hopping between Fe3+, Ni3+, Fe4+, and Ni4+, giving average charges of Fe3+S and Ni3+S. These solids are the subject of ongoing research. 

Organic electroreductive coupling reactions using transition-metal complexes as catalysts have been widely investigated. Reviews on the subject have been published [89, 90]. The method involving the most common transition-metal complexes (nickel, cobalt, palladium) appears to be a useful tool to synthetize heterocycles from organic halides via radical intermediates. Nickel catalyst precursors are nickel(II) salts that are cathodically reduced either to nickel(I) or to nickel(O) and cobalt catalyst... 

Recently, chloro-, bromo-, and iodoben-zenes have been subjected to electroreduction using Ni(0) complex mediators to yield biphenyl. NiCl2L2 and NiBr2L2 [L= P(Ph)3, (Ph)2PCH2CH2P(Ph)2] have been used as catalysts [259-265]. Pro-tic media such as alcohols, that is, methanol, ethanol or alcohol-water mixtures are found to be suitable solvents for achieving the electrosynthesis of biaryls from aryl halides according to a procedure that involves a catalytic process by nickel-2,2 -bipyridine complexes [266]. Electrochemical cross-coupling between... 

Samples of metal complexes isolated from the final solutions were subjected to microanalysis (for carbon, hydrogen, oxygen, and sulfur). Metals were determined colorimetrically by the following methods— copper as the complex formed with sodium diethyl dithiocarbamate (6) cobalt as the nitroso-R salt complex (7) nickel as the dimethylglyoxime complex (4). 

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