Borderline cation

Potentially toxic compounds in the subsurface, such as Cd ", Pb ", or Hg ", which are generally found in very low concentrations, are considered soft cations (Buffle 1988). These ions have strong affinity to intermediate and soft ligands and therefore bond to them covalently. Borderline cations, which embrace transition metals like Cu and Ztfexhibit affinity for the soft cations as well as for alkaline-earth compounds. The order of donor atom affinity for soft metals is O < N < S. Functional groups present in subsurface organic matter that show affinity for soft and borderline metals are shown in Table 14.2. 

Fig. 3. Correlations between ionic index (z2//) and complexation constants log10 /3f for (a) the monohydroxo, (b) the monofluorido, and (c) the monosulphato complexes of hard cations and the borderline cation Ni(II).

The borderline cations comprise the first row of transition metals, in their common oxidation states, as well as Ga, In " ", Cd, Sn " ", and Pb ". The hydrogen ion and the metalloid ions As(III) and Sb(III) are also included in this category (Nieboer and Richardson 1980). They are able to form stable complexes with numerous ligands, and preference for a given donor group... 

Monovalent cations are compatible with CMC and have Httle effect on solution properties when added in moderate amounts. An exception is sUver ion, which precipitates CMC. Divalent cations show borderline behavior and trivalent cations form insoluble salts or gels. The effects vary with the specific cation and counterion, pH, DS, and manner in which the CMC and salt are brought into contact. High DS (0.9—1.2) CMCs are more tolerant of monovalent salts than lower DS types, and CMC in solution tolerates higher quantities of added salt than dry CMC added to a brine solution. 

Many other cations besides the norbomyl cation have nonclassical structures. Scheme 5.5 shows some examples which have been characterized by structural studies or by evidence derived from solvolysis reactions. To assist in interpretation of the nonclassical stmctures, the bond representing the bridging electron pair is darkened in a corresponding classical stmcture. Not surprisingly, the borderline between classical stmctures and nonclassical stmctures is blurred. There are two fundamental factors... 

In reactions in which separated ion pairs are involved, e.g., R4N+, K or Na +, and as a borderline case, Li +, the cation does not contribute to the adjustment of the reaction partners in a dense, well-ordered transition state poor selcctivities arc usually the result of these carbanionic carbonyl additions. Further, the high basicity of such carbanionic species may cause decomposition or racemization of sensitive reactions partners. 

Szele and Zollinger (1978 b) have found that homolytic dediazoniation is favored by an increase in the nucleophilicity of the solvent and by an increase in the elec-trophilicity of the P-nitrogen atom of the arenediazonium ion. In Table 8-2 are listed the products of dediazoniation in various solvents that have been investigated in detail. Products obtained from heterolytic and homolytic intermediates are denoted by C (cationic) and R (radical) respectively for three typical substituted benzenediazonium salts and the unsubstituted salt. A borderline case is dediazoniation in DMSO, where the 4-nitrobenzenediazonium ion follows a homolytic mechanism, but the benzenediazonium ion decomposes heterolytically, as shown by product analyses by Kuokkanen (1989) the homolytic process has an activation volume AF = + (6.4 0.4) xlO-3 m-1, whereas for the heterolytic reaction AF = +(10.4 0.4) x 10 3 m-1. Both values are similar to the corresponding activation volumes found earlier in methanol (Kuokkanen, 1984) and in water (Ishida et al., 1970). 

Aluminum forms a complete series of AlYX compounds (Y = S, Se, Te X = Cl, Br, I). Furthermore, a number of compounds with Se(IV) and Te(IV) are known, such as TeClJ AlClj (197) and SeClJ AICI4 (364), which are not considered here. A borderline case consists in the reduced phases found in the systems (TeCl4-(-4AlCl3)-Te and (SeCl4 + 4A1C13)-Se (88), e.g., Te (AlCl4-)2 (89), Te + (Al Clf)2 (89), Te + (AlCli-) (88), Se5+ (AlClj) (88), and Se + (AlClj)2 (87), which contain cyclic pol3dellurium and polyselenium cations. For a detailed review of homopolyatomic ions of the posttransition elements, see (86). 

It also turns out from the reduction potentials of [112" ], [25" ], [99 ], [100 ], [26 ] and [IIS" ] (Table 8) that the product of the reaction, a covalent compound or a salt with [2 ], changes abruptly from a covalent compound to a salt as the stability of the cation moiety is gradually increased. The borderline between the two types of reactions lies between [100" ] and [26 ]. The difference (0.017 V) in the E ed values of these cations suggests that only a slight difference (0.4 kcal mol or less) in electronic stability can completely switch the type of bond. 

The focus of the next four chapters (Chapters 14-17) is mainly on the theoretical/computational aspects. Chapter 14 by T. S. Sorensen and E. C. F. Yang examines the involvement of p-hydrido cation intermediates in the context of the industrially important heptane to toluene dehydrocyclization process. Chapter 15 by P. M. Esteves et al. is devoted to theoretical studies of carbonium ions. Chapter 16 by G. L. Borosky and K. K. Laali presents a computational study on aza-PAH carbocations as models for the oxidized metabolites of Aza-PAHs. Chapter 17 by S. C. Ammal and H. Yamataka examines the borderline Beckmann rearrangement-fragmentation mechanism and explores the influence of carbocation stability on the reaction mechanism. 

A number of important issues involving the structure and dynamics of ionically conducting polymers have yet to receive thorough theoretical consideration. For example, in the case df multivalent cations, some systems exhibit cation transport whereas others do not, due to strong cation solvation. Therefore a term associated with ion-polymer dissociation must be important in systems which are on the borderline between these two extremes. This term is likely to be of the form ikHi, /2RT). 

Lifetimes are longer in the more weakly nucleophilic TFE and HFIP, and cations whose existence is on the borderline in water and simple alkanols can become quite long lived, especially in HFIP. Benzenium ions such as protonated mesitylene can also be observed in HFIP, and there is an estimate for a simple secondary cation 77 60 pjjgj.g Qjjg estimate of the lifetime of an acylium ion (72), based upon the clock approach. Even with the powerful electron-donor 4-Me2N on the aromatic ring, this cation appears to be very short lived in water. 

The peroxidase reaction is coupled with the formation of free radicals, either directly at the protein backbone or at the porphyrin moiety or both. This topic is borderline to the scope of this review and we will restrict ourselves to those studies which have at least a strong connection with the heme iron situation. We mention however, some relevant articles which have appeared in the period reviewed. Specific interest was given to a bi-functional enzyme from Mycobacterium tuberculosis which has both catalase and peroxidase activity.286-287,288-289 We also mention that a critical role of cations like Ca2+ and K+ has been described.290-291... 

Similarly, relevant electrophiles (Lewis acids) including A-type metal cations (hard), bivalent transition metal ions (borderline), and B-type metal ions (soft) can be categorized (see Stumm and Morgan 1996). Note that in organic molecules, the atom where a nucleophile attacks (i.e., the electrophilic site) may possess harder (e.g., C=0, P=0) or softer (e.g., CH3-X) character. 

Solvent effects on the dissociation of 11 2,6-disubstituted benzoic acids have been analysed by chemometric analysis.66 The acid-base behaviour of the three zwitterionic pyridinecarboxylic acids (picolinic, nicotinic, and isonicotinic acid) has been studied. The cationic form of picolinic acid converts partially into the corresponding zwitterion within a borderline acidity range (pH/acidity function). The various pXa values were determined for the three isomers by spectrophotometric and potentiometric methods and reasonable agreement was found.67... 

Another troublesome borderline area is that between ionic solids and three-dimensional polymers. The distinction cannot be made from the structure alone. Electrical conductivity in the molten state does not, as already mentioned, necessarily demonstrate the presence of ions in the solid state and such a test is inapplicable where, as often happens, the substance sublimes or decomposes before melting. There can rarely be any objective means of assigning a compound to one category or the other. We are often persuaded towards one description on aesthetic grounds. For example, the structure of sodium chloride cannot easily be rendered in terms of localised, electron-pair bonds (but this is true also of many unequivocally covalent compounds). Its structure is eminently plausible for an array of cations and anions, however. 

---