Covalent bonds cations

Obviously sufficient energy is available to break the A1—Cl covalent bonds and to remove three electrons from the aluminium atom. Most of this energy comes from the very high hydration enthalpy of the AP (g) ion (p. 78). Indeed it is the very high hydration energy of the highly charged cation which is responsible for the reaction of other essentially covalent chlorides with water (for example. SnCl ). 

The biochemical basis for the toxicity of mercury and mercury compounds results from its ability to form covalent bonds readily with sulfur. Prior to reaction with sulfur, however, the mercury must be metabolized to the divalent cation. When the sulfur is in the form of a sulfhydryl (— SH) group, divalent mercury replaces the hydrogen atom to form mercaptides, X—Hg— SR and Hg(SR)2, where X is an electronegative radical and R is protein (36). Sulfhydryl compounds are called mercaptans because of their ability to capture mercury. Even in low concentrations divalent mercury is capable of inactivating sulfhydryl enzymes and thus causes interference with cellular metaboHsm and function (31—34). Mercury also combines with other ligands of physiological importance such as phosphoryl, carboxyl, amide, and amine groups. It is unclear whether these latter interactions contribute to its toxicity (31,36). 

A reactive dye for ceUulose contains a chemical group that reacts with ionized hydroxyl ions in the ceUulose to form a covalent bond. When alkaH is added to a dyebath containing ceUulose and a reactive dye, ionization of ceUulose and the reaction between dye and fiber is initiated. As this destroys the equihbrium more dye is then absorbed by the fiber in order to re-estabUsh the equUibrium between active dye in the dyebath and fiber phases. At the same time the addition of extra cations, eg, Na+ from using Na2C02 as alkaH, has the same effect as adding extra salt to a direct dye. Thus the addition of alkaH produces a secondary exhaustion. 

Scheme 1. (a) Formation of a fragment with m/z = 247 from a covalent bond between y-GPS and DBA dimer, (b) Final structure of the cation with mjz = 247. Reproduced by permission of the American Chemical Society from Ref. [55]. 

The pyrylium cation possesses, according to the substituents in positions 2, 4, and 6, a more or less pronounced electrophilic reactivity which enables it to add nucleophiles in these positions. According to the nucleophilic reactivity and the carbon basicity " of the anions, an ion pair (a substituted pyrylium cation and an anion halide, perchlorate, sulfate, fluoroborate, chloroferrate, etc.), or a covalently bonded 2H- or 4//-pyran may be formed. With the more basic anions... 

Complex ions used for electroplating are anions. The cathode tends to repel them, and their transport is entirely by diffusion. Conversely, the field near the cathode assists cation transport. Complex cyanides deserve some elaboration in view of their commercial importance. It is improbable that those used are covalent co-ordination compounds, and the covalent bond breaks too slowly to accommodate the speed of electrode reactions. The electronic structure of the cyanide ion is ... 

Diagrams of four types of substances (see text discussion). X represents a nonmetal atom, — represents a covalent bond, M+ a cation, X- an anion, and e an electron. 

In principle, any molecule or anion with an unshared pair of electrons can act as a Lewis base. In other words, it can donate a lone pair to a metal cation to form a coordinate covalent bond. In practice, a ligand usually contains an atom of one of die more electronegative elements (C, N, O, S, F, Cl, Br, I). Several hundred different ligands are known. Those most commonly encountered in general chemistry are NH3 and HzO molecules and CN , Cl-, and OH- ions. 

Hg22+ is a polyatomic cation there is a covalent bond between the mercury atoms. 

The transition metals, unlike those in Groups 1 and 2, typically show several different oxidation numbers in their compounds. This tends to make their redox chemistry more complex (and more colorful). Only in the lower oxidation states (+1, +2, +3) are the transition metals present as cations (e.g., Ag+, Zn2+, Fe3+). In higher oxidation states (+4 to +7) a transition metal is covalently bonded to a nonmetal atom, most often oxygen. 

A slight but systematic decrease in the wave number of the complexes bond vibrations, observed when moving from sodium to cesium, corresponds to the increase in the covalency of the inner-sphere bonds. Taking into account that the ionic radii of rubidium and cesium are greater than that of fluorine, it can be assumed that the covalent bond share results not only from the polarization of the complex ion but from that of the outer-sphere cation as well. This mechanism could explain the main differences between fluoride ions and oxides. For instance, melts of alkali metal nitrates display a similar influence of the alkali metal on the vibration frequency, but covalent interactions are affected mostly by the polarization of nitrate ions in the field of the outer-sphere alkali metal cations [359]. 

Alpert has shown [47] that poly(succinimide)-silica can be further hydrolyzed to poly (aspartic acid)-silica or condensed with [3-alanine in aqueous solution to form a covalently bonded copolymer of 2-carboxyethyl aspartamide and aspartic acid. The content of carboxyl groups generated by this way has not been quantified directly, but the cation-exchange hemoglobin capacity has been measured for a series of the packings. Thus, the optimal concentration of poly(succinimide) used in the synthesis was found to be 2 5%. 

Whether or not the highly electropositive alkali metals or magnesium form an ionic instead of a covalent bond to the oxygen of the enolate is less important. Even if there is a contact ion pair of the metal cation and the oxygen anion, the geometry of the six-membered chair transition state, as outlined above, will be maintained. 

Because nonmetals do not form monatomic cations, the nature of bonds between atoms of nonmetals puzzled scientists until 1916, when Lewis published his explanation. With brilliant insight, and before anyone knew about quantum mechanics or orbitals, Lewis proposed that a covalent bond is a pair of electrons shared between two atoms (3). The rest of this chapter and the next develop Lewis s vision of the covalent bond. In this chapter, we consider the types, numbers, and properties of bonds that can be formed by sharing pairs of electrons. In Chapter 3, we revisit Lewis s concept and see how to understand it in terms of orbitals. 

To remove an ion, we can use the fact that many metal cations are Lewis acids (Section 10.2). When a Lewis acid and a Lewis base react, they form a coordinate covalent bond and the product is called a coordination complex. In this section, we consider complexes in which the Lewis acid is a metal cation, such as Ag+. An example is the formation of Ag(NI 1,)2+ when an aqueous solution of the Lewis base ammonia is added to a solution of silver ions ... 

Hydrogen is unusual because it can form both a cation (1I+) and ail anion (11 ). Moreover, its intermediate electronegativity (2.2 on the Pauling scale) means that it can also form covalent bonds with all the nonmetals and metalloids. Because hydrogen forms compounds with so many elements (Table 14.2 also see Section 14.2), we shall meet more of its compounds when we study the other elements. 

In compounds, mercury has the oxidation number +1 or +2. Its compounds with oxidation number +1 are unusual in that the mercury(I) cation is the covalently bonded diatomic ion (Hg—Hg)2+, written Hg22+. 

B Aluminum forms an amphoteric oxide in which it has the oxidation state +3 therefore, aluminum is the element. 14.3B Hydrogen is a nonmetal and a diatomic gas at room temperature. It has an intermediate electronegativity (x — 2.2), so it forms covalent bonds with nonmetals and forms anions in combination with metals. In contrast, Group 1 elements are solid metals that have low electronegativities and form cations in combination with nonmetals. 

These ions represent strong nucleophiles which form a covalent bond during recombination with the methyl cation. The resulting CH3—X should be relatively less reactive when attacked by a nucleophile. 

The concept of silicates as inorganic polymers was implicit in the ideas developed by W. H. Zacheriasen in the early 1930s. He conceived of silicates as consisting of macromolecular structures held together by covalent bonds but including network-dwelling cations. These cations were not assumed to have a structural role but merely to be present in order to balance the charges on the anionic polymer network. 

When the tritium (half-life 12.26 years) decays it is converted to the helium-3 isotope, which, of course, does not form covalent bonds, and so immediately departs, leaving behind the alkynyl cation. When this was done in the presence of benzene, RC CCgHs was isolated. The tritium-decay technique has also been used to generate vinylic and aryl cations. 

Triphenylphosphonium ylide reacts with the silylene complex 93 which has a highly electrophilic silicon center, to give the corresponding cationic adduct 94 [115]. The lengthening of the PC bond indicates a loss of the double bond character of the ylide and corresponds to the formation of a tetrahedral silicon center with four covalent bonds (Scheme 28). 

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