Transition metal ions different metals

The wide possibilities to synthesize and/or to modify all kinds of zeolites such as they present channel networks which differ by their spatial distribution (allowing more or less the circulation of hydrocarbons) and by their size, such as they may bear active sites at different locations (acidic sites, catalytically active transition metal ions, entrapped metallic particles or clusters...) make the zeolite future look bright. At the present time it... 

A major concern has been the contamination of the soil by transition metal ions ( heavy metals ) that may leach out of degrading polyolefins after repeated use of the same formulation on the same soil. This is to a large extent a function of the low molecular weight additives used in the polymer. However, agricultural soils already vary enormously in transition metal content. Nickel has been studied in some detail because it is used in a number of plastics products and concern has been expressed about its environmental toxicity and possible accumulation in growing plants. Table 3 shows the concentrations of Ni in different types of soils. It is clear that some common soils, notably limestone, contain very considerable concentrations of nickel but no health hazards have been reported in... 

Cobalt exists in the +2 or +3 valence states for the majority of its compounds and complexes. A multitude of complexes of the cobalt(III) ion [22541-63-5] exist, but few stable simple salts are known (2). Werner s discovery and detailed studies of the cobalt(III) ammine complexes contributed gready to modem coordination chemistry and understanding of ligand exchange (3). Octahedral stereochemistries are the most common for the cobalt(II) ion [22541-53-3] as well as for cobalt(III). Cobalt(II) forms numerous simple compounds and complexes, most of which are octahedral or tetrahedral in nature cobalt(II) forms more tetrahedral complexes than other transition-metal ions. Because of the small stabiUty difference between octahedral and tetrahedral complexes of cobalt(II), both can be found in equiUbrium for a number of complexes. Typically, octahedral cobalt(II) salts and complexes are pink to brownish red most of the tetrahedral Co(II) species are blue (see Coordination compounds). 

Most of the free-radical mechanisms discussed thus far have involved some combination of homolytic bond dissociation, atom abstraction, and addition steps. In this section, we will discuss reactions that include discrete electron-transfer steps. Addition to or removal of one electron fi om a diamagnetic organic molecule generates a radical. Organic reactions that involve electron-transfer steps are often mediated by transition-metal ions. Many transition-metal ions have two or more relatively stable oxidation states differing by one electron. Transition-metal ions therefore firequently participate in electron-transfer processes. 

It is evident [see Eq. (5), Section II[] that for catalysts of the same or similar composition the number of active centers determined must be consistent with the catalytic activity it can be expected that only in the case of highly active supported catalysts a considerable part of the surface transition metal ions will act as propagation centers. However, the results published by different authors for chromium oxide catalysts are hardly comparable, as the polymerization parameters as a rule were very different, and the absolute polymerization rate was not reported. 

Crystal-field theory (CFT) was constructed as the first theoretical model to account for these spectral differences. Its central idea is simple in the extreme. In free atoms and ions, all electrons, but for our interests particularly the outer or non-core electrons, are subject to three main energetic constraints a) they possess kinetic energy, b) they are attracted to the nucleus and c) they repel one another. (We shall put that a little more exactly, and symbolically, later). Within the environment of other ions, as for example within the lattice of a crystal, those electrons are expected to be subject also to one further constraint. Namely, they will be affected by the non-spherical electric field established by the surrounding ions. That electric field was called the crystalline field , but we now simply call it the crystal field . Since we are almost exclusively concerned with the spectral and other properties of positively charged transition-metal ions surrounded by anions of the lattice, the effect of the crystal field is to repel the electrons. 

Organic Molecules It can be seen from our earlier discussion that the presence of a transition metal ion is not always required for an electrochromic effect. Indeed, many organic molecules can yield colored products as a result of reversible reduction or oxidation. 4,4 -Bipyridinium salts are the best known example of such compounds. These compounds can be prepared, stored, and purchased in colorless dicationic form (bipm +). One electron reduction of the dication leads to the intensely colored radical cation (bipm+ ). Such radical cations exist in equilibrium with their dimers (bipm ). In the case of methyl viologen, the radical cation is blue and the dimer is red. By varying the substient group in the molecule, different colors can be obtained. 

Bond length differences between HS and LS isomers have been determined for a number of iron(II), iron(III) and cobalt(II) complexes on the basis of multiple temperature X-ray diffraction structure studies [6]. The available results have been collected in Table 17. Average values for the bond length changes characteristic for a particular transition-metal ion have been extracted from these data and are obtained as AR 0.17 A for iron(II) complexes, AR 0.13 A for iron(III) complexes, and AR = 0.06 A for cobalt(II) complexes. These values may be compared with the differences of ionic radii between the HS and LS forms of iron(II), iron(III) and cobalt(II) which were estimated some time ago [184] as 0.16, 0.095, and 0.085 A, respectively. 

The ability of transition metal ions, and especially chromium (as Cr3+), to form very stable metal complexes may be used to produce dyeings on protein fibres with superior fastness properties, especially towards washing and light. The chemistry of transition metal complex formation with azo dyes is discussed in some detail in Chapter 3. There are two application classes of dyes in which this feature is utilised, mordant dyes and premetallised dyes, which differ significantly in application technology but involve similar chemistry. 

More than 3000 different enzymes have been extracted from animals, plants and microorganisms. Traditionally, they have been used in impure form since purification is expensive and pure enzymes may be difficult to store and use. There is usually an optimum temperature and pH for maximum activity of an enzyme. Outside these optimum conditions, activity may simply be held in check or the enzyme may become denatured , i.e. altered in such a way that activity is lost permanently, although some forms of denaturing are reversible. Many enzymes are also sensitive to transition-metal ions, the effect being specific to particular metal ions and enzymes. In some cases, certain metal ions are essential for the stability and/or activity of an enzyme. In other cases, metal ions may inhibit the activity of an enzyme. Similarly, certain organic compounds can act as enzyme inhibitors or activators. 

Many organic and inorganic compounds, fibers, and particles are capable of damaging nucleic acids by generating reactive oxygen species via the reduction of dioxygen. These stimuli include different classes of organic compounds, classic prooxidants (anticancer antibiotics, various quinones, asbestos fibers, and so on), and even antioxidants, which can be oxidized in the presence of transition metal ions. 

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