Cobalt complexes reactivity

Although the actual reaction mechanism of hydrosilation is not very clear, it is very well established that the important variables include the catalyst type and concentration, structure of the olefinic compound, reaction temperature and the solvent. used 1,4, J). Chloroplatinic acid (H2PtCl6 6 H20) is the most frequently used catalyst, usually in the form of a solution in isopropyl alcohol mixed with a polar solvent, such as diglyme or tetrahydrofuran S2). Other catalysts include rhodium, palladium, ruthenium, nickel and cobalt complexes as well as various organic peroxides, UV and y radiation. The efficiency of the catalyst used usually depends on many factors, including ligands on the platinum, the type and nature of the silane (or siloxane) and the olefinic compound used. For example in the chloroplatinic acid catalyzed hydrosilation of olefinic compounds, the reactivity is often observed to be proportional to the electron density on the alkene. Steric hindrance usually decreases the rate of... 

With sp bond angles calculated to be around 162°, macrocycle 131 would be highly strained and was therefore expected to be quite reactive [79]. The octa-cobalt complex 132, on the other hand, should be readily isolable. Indeed, 132 was prepared easily from 133 in five steps, and was isolated as stable, deep maroon crystals (Scheme 30). All spectroscopic data supported formation of the strain-free dimeric structure. Unfortunately, all attempts to liberate 132 from the cobalt units led only to insoluble materials. Diederich et al. observed similar problems when trying to prepare the cyclocarbons [5c]. Whether the failure to prepare these two classes of macrocycles is due to the extreme reactivity of the distorted polyyne moiety or to the lack of a viable synthetic route is not certain. Thus, isolation and characterization of smaller bent hexatriyne- and octatetrayne-containing systems is an important goal that should help answer these questions. 

The third class of metal catalysts includes nickel and cobalt complexes of Schiff bases and nitrogen macrocyclic ligands, which can form on electroreduction cobalt(I) and nickel(I) reactive intermediates for the activation of organic halides. 

The high reactivity of the cobalt-complexed propargylic systems has also allowed for ether oxygens to serve as nucleophiles, which has led to the fashioning of medium-sized ring ethers via ring expansion (Equation (60)), and also... 

Mixed chromium/cobalt complexes in reactive dyes... 

At present, synthetic routes to more than 40 metal complexes other than the copper complex are known. Apart from a cobalt phthalocyanine pigment (P.B.75) which was introduced to the market just recently, none of the resulting products, however, has stimulated commercial interest as a pigment. Nickel complexes, however, are found in reactive dyes, while cobalt complexes of this basic structure are employed as developing dyes. 

The strength of the cobalt-carbon bond is very much influenced by the nature of the other five ligands. If these ligands are varied, cobalt complexes may be obtained having different reactivities of the Co-C bond (45). 

The y-lactone-type cobalt complexes described in Section III,A have further been studied with regard to spectroscopy (317), reactivity... 

Both 2 1 chromium and cobalt complex azo dyestuffs have little or no affinity for cellulosic fibres and until the early 1960s their use was restricted to wool and nylon. With the introduction by ICI of their Procion range of fibre-reactive dyes, however, their use was extended to cellulosic fibres on which they give prints having excellent fastness to light and wet treatments. Before that time the development of metal complex dyes for cellulose had followed a similar pattern to that of the development of such dyes for wool but, in this case, the most important metal was copper. Early work in this field has been reviewed by several authors.1 The after-treatment of dyeings on cotton obtained from dyestuffs such as (11) with copper salts was used for many years to improve fastness... 

Chromium and cobalt are the metals most commonly used in dyestuffs for polyamide fibres and leather because of their kinetic inertness and the stability of their complexes towards acid. Since the advent of fibre-reactive dyestuffs, chromium and cobalt complexes have also found application as dyestuffs for cellulosic fibres, particularly as black shades of high light-fastness. Copper complexes are of more importance as dyes for cellulosic fibres and are unsuitable for polyamide fibres because of their rather low stability towards acid treatments. 

The porphyrin-cobalt complex gives rise to the cation radical with charge spin localization at the nitrogen atom of the porphyrin ring. The cation radical thus formed acquires enhanced reactivity and can add tolane (Kochi 1986), Scheme 1-52. The main point... 

Acyclic /V-alkylimines, asymmetric hydrogenation, 10, 56 Acyclic ( j3-allyl)cobalt complexes, oxidation reactions, 7, 58 Acyclic allylic esters, alkylation, 11, 76 Acyclic aromatic imines, asymmetric hydrogenation, 10, 56 Acyclic 1-buly l-( )5-pencadienyl) iron cations, preparation and reactivity, 6, 156... 

As opposed to copper complex dyes, 1 2 chromium and cobalt complexes can only be bound to cotton if a fiber-reactive group is incorporated in the dye backbone [32], For example, the reactive 1 2 chromium-cobalt complex 20 C.I. Reactive Black 8, 18207 M = Cr/Co = ca. 3 1 M = Cr [ 79828-44-7] M = Co [79817-89-3] provides black prints on cotton, whereby the corresonding pure 1 2 chromium... 

The second-order rate constants for reactions of Co(I)(BDHC) with alkyl halides were determined spectrophotometrically at 400 nm (17). These rate constants are listed in Table VII along with those for Co(I)(corrinoid)(vitamin Bi2s) in methanol at 25°C (35). These data indicate that the SN2 mechanism is operative in the reaction of Co(I)(BDHC) the iodides are more reactive with the cobalt complex than the bromides, and the rate decreases with increasing bulkiness of the alkyl donor. The steric effect is more pronounced for Co(I)(BDHC) than for vitamin B12s, which is confirmed by the rate ratios for... 

Modified carbonylcobalt complexes can catalyze the PKR. One or more CO can be substituted by phosphines, and these can be immobilized in resins thus giving anchored cobalt complexes (27), that were able to catalyze the reaction of 28 giving 29 with good yield and minor amounts of 30 (Scheme 10) [76]. Other cobalt metal clusters like Co4(CO)i2 [77] or methyl-idynetricobalt nonacarbonyl [78] have exhibited high reactivity in the catalytic PKR. 

The coordination chemistry of cobalt can be summed up in three words synthesis, structure and reactivity, with synthesis being the most important because it comes first. This chapter concentrates on synthetic aspects and its aim is to provide the reader with starting points to the preparation of cobalt complexes in addition to surveying their chemistry. 

The reactivity of alkylidyne compounds has also been widely studied, particularly by Seyferth and co-workers who have carried out a great variety of reactions with cobalt complexes (303-312). Other groups... 

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