Transition-metal cations

Simplest examples are prepared by the cyclic oligomerization of ethylene oxide. They act as complexing agents which solubilize alkali metal ions in non-polar solvents, complex alkaline earth cations, transition metal cations and ammonium cations, e.g. 12—crown —4 is specific for the lithium cation. Used in phase-transfer chemistry. ... 

Despite the weak basicity of isoxazoles, complexes of the parent methyl and phenyl derivatives with numerous metal ions such as copper, zinc, cobalt, etc. have been described (79AHC(25) 147). Many transition metal cations form complexes with Imidazoles the coordination number is four to six (70AHC(12)103). The chemistry of pyrazole complexes has been especially well studied and coordination compounds are known with thlazoles and 1,2,4-triazoles. Tetrazole anions also form good ligands for heavy metals (77AHC(21)323). 

Lewis acids are defined as molecules that act as electron-pair acceptors. The proton is an important special case, but many other species can play an important role in the catalysis of organic reactions. The most important in organic reactions are metal cations and covalent compounds of metals. Metal cations that play prominent roles as catalysts include the alkali-metal monocations Li+, Na+, K+, Cs+, and Rb+, divalent ions such as Mg +, Ca +, and Zn, marry of the transition-metal cations, and certain lanthanides. The most commonly employed of the covalent compounds include boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Various other derivatives of boron, aluminum, and titanium also are employed as Lewis acid catalysts. 

The best characterized of these reactions involve the mercuric ion, Hg ", as the cation. The same process occurs for other transition-metal cations, especially Pd, but the products often go on to react fiirther. Synthetically important reactions involving Pd will be discussed in Section 8.2 of Part B. The mercuration products are stable, and this allows a relatively uncomplicated study of the addition reaction itself The usual nucleophile is the solvent, either water or an alcohol. The tenn oxymercuration is used to refer to reactions in... 

As, Si, etc.) which are able to act as ligands to a variety of transition metal cations as well as to organometallic groups such as SnR, AsR and Ti (h -CsHs). 

Yosida et al. [41] found that p-t< rr-butylcalix[6]ar-ene can extract Cu from the alkaline-ammonia solution to the organic solvent. Nagasaki and Shinkai [42] described the synthesis of carboxyl, derivatives of calix-[n]arenes ( = 4 and 6) and their selective extraction capacity of transition metal cations from aqueous phase to the organic phase. Gutsche and Nam [43] have synthesized various substituted calix[n]arenes and examined the complexes of the p-bromo benzene sulfonate of p-(2-aminoethyl)calix[4]arene with Ni, Cu , Co-, and Fe. ... 

Based on the above results they have concluded that the ligand groups circularly arranged on the lower rim of the calixarene cavity construct a novel cyclic metal receptor for selective extraction of transition metal cations. Results suggest that the fine tuning in molecular... 

Recently, Deligoz and Yilmaz [51] prepared three polymeric calix[4]arenes, which were synthesized by reacting chloromethylated polystyrene with 25,26,27-tribenzoyloxy-28-hydroxy calix[4]arene (2a, 3a) and po-lyacryloyl chloride with 25,26,27,28-tetraacetoxy ca-lix[4]arene (4a). After alkaline hydrolysis of the polymers, they were utilized for selective extraction of transition metal cations from aqueous phase to organic phase. 

Deligoz and Yilmaz [52] reported that the selective liquid-liquid extraction of various alkali and transition metal cations from the aqueous phase to the organic phase as carried out by using p-tert-h iy calix[4]arene (1), p-tert-b x. y calix[6]arene (2), tetra-ethyl-p-tm-butylcalix[4]arene-tetra-acetate (3), tetra-methyl-p-/< /-/-butyl calix[4]arene-tetraketone (4), calix[n]arenes ( = 4 and 6) bearing oxime groups on the lower rim (5 and 6) and a polymeric calix(4]arene (8). It was found that compounds 5 and 6 showed selectivity towards Ag, Hg, Hg, Cu, and Cr and the order of the ex-tractability was Hg > Hg > Ag > Cu > Cr. The polymeric calix[4]arene (8) was selective for Ag, Hg, and Hg , unlike its monomeric analog. 

A certain crown ether having additional coordination sites for a trasition metal cation (71) changes the transport property for alkali metal cations when it complexes with the transition metal cation 76) (Fig. 13). The fact that a carrier can be developed which has a reversible complexation property for a transition metal cation strongly suggests that this type of ionophore can be applied to the active transport system. 

Similar relationships hold for ionic solids containing polyatomic ions (Table 2.2) or transition metal cations (Figure 4.2). 

In transition metal cations, 3d is lower in energy than 4s. 

Recall (page 150) that in a simple transition metal cation—... 

In the uncomplexed transition metal cation, all of these orbitals have the same energy. 

Give the electron configuration and/or orbital diagram of a transition metal cation. 

Using the data in this table and in Table 18.1 (page 487), it is possible to decide on the relative stabilities of different transition metal cations in water solution. 

Table 20.4 Ease of Reduction ed (V) of Transition Metal Cations ...

As you can judge from Table A, transition metal cations are frequently found in enzymes. The Zn2+ ion alone is known to be a component of at least 70 different enzymes. One of these, referred to as "alcohol dehydrogenase," is concentrated in the liver, where it acts to break down alcohols. Another zinc-containing enzyme is involved in the normal functioning of oil glands in the skin, which accounts for the use of Zn2+ compounds in the treatment of acne. 

Second, metal atoms carry some positive charge in the majority of their compounds. Transition metal cations have pure d configurations, in contrast to the mixed d-s configurations of free neutral transition metal atoms. There is the chemical rule that "s electrons fall down into the d level... 

Use the aufbau approach, remembering that because Cr is a transition metal cation, its 3 d orbital is more stable than is its 4 S orbital. 

Although naturally occurring compounds of transition metals are restricted in scope, a wide variety of compounds can be synthesized in the laboratory. Representative compounds appear in Table 20-2. These compounds fall into three general categories There are many binary halides and oxides in a range of oxidation numbers. Ionic compounds containing transition metal cations and polyatomic oxoanions also are common these include nitrates, carbonates, sulfates, phosphates, and perchlorates. Finally, there are numerous ionic compounds in which the transition metal is part of an oxoanion. 

C20-0035. Write valence electron configurations for the following transition metal cations (a) (b)... 

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