Inorganic chemistry complex ions

Surfactants have also been of interest for their ability to support reactions in normally inhospitable environments. Reactions such as hydrolysis, aminolysis, solvolysis, and, in inorganic chemistry, of aquation of complex ions, may be retarded, accelerated, or differently sensitive to catalysts relative to the behavior in ordinary solutions (see Refs. 205 and 206 for reviews). The acid-base chemistry in micellar solutions has been investigated by Drummond and co-workers [207]. A useful model has been the pseudophase model [206-209] in which reactants are either in solution or solubilized in micelles and partition between the two as though two distinct phases were involved. In inverse micelles in nonpolar media, water is concentrated in the micellar core and reactions in the micelle may be greatly accelerated [206, 210]. The confining environment of a solubilized reactant may lead to stereochemical consequences as in photodimerization reactions in micelles [211] or vesicles [212] or in the generation of radical pairs [213]. 

When a Br nsted base functions catalytically by sharing an electron pair with a proton, it is acting as a general base catalyst, but when it shares the electron with an atom other than the proton it is (by definition) acting as a nucleophile. This other atom (electrophilic site) is usually carbon, but in organic chemistry it might also be, for example, phosphorus or silicon, whereas in inorganic chemistry it could be the central metal ion in a coordination complex. Here we consider nucleophilic reactions at unsaturated carbon, primarily at carbonyl carbon. Nucleophilic reactions of carboxylic acid derivatives have been well studied. These acyl transfer reactions can be represented by... 

This chapter is devoted to complex ions and the important role they play in inorganic chemistry. We consider in turn—... 

The basic ideas concerning the structure and geometry of complex ions presented in this chapter were developed by one of the most gifted individuals in the history of inorganic chemistry,... 

This chapter describes several Important applications of aqueous equilibria. We begin with a discussion of buffer chemistry, followed by a description of acid and base titration reactions. Then we change our focus to examine the solubility equilibria of inorganic salts. The chapter concludes with a discussion of the equilibria of complex Ions. 

Guilbault GG, Scheide EP. 1970. Chemisorption reactions of diisopropyl methyl phosphonate with various metal salts and the effect of complex-ion formation on the phosphorus-oxygen stretching frequency. Journal of Inorganic and Nuclear Chemistry 32(9) 2959-2962. 

During the study of inorganic chemistry, the structures for a large number of molecules and ions will be encountered. Try to visualize the structures and think of them in terms of their symmetry. In that way, when you see that Pt2+ is found in the complex PtCl42 in an environment described as D4h, you will know immediately what the structure of the complex is. This "shorthand" nomenclature is used to convey precise structural information in an efficient manner. Table 5.1 shows many common structural types for molecules along with the symmetry elements and point groups of those structures. 

Perhaps the greatest area in which the Lewis acid-base approach is most useful is that of coordination chemistry. In the formation of coordination compounds, Lewis acids such as Cr3+, Co3+, Pt2+, or Ag+ bind to a certain number (usually 2, 4, or 6) of groups as a result of electron pair donation and acceptance. Typical electron pair donors include H20, NH3, F , CN , and many other molecules and ions. The products, known as coordination compounds or coordination complexes, have definite structures that are predictable in terms of principles of bonding. Because of the importance of this area of inorganic chemistry, Chapters 16 through 22 in this book are devoted to coordination chemistry. 

Coordination complexes of cobalt(III) are ideal for undergraduate work in inorganic chemistry because of the inert nature of the d6 ion. The first synthesis of this trans complex was performed in 1896 by S. M. Jorgenson and took approximately 96 h.1 The synthesis described herein takes approximately 15 min once the starting material, [Co(NH3)4C03]N03, has been prepared by known procedures.2... 

Chem. 29 (1967), pp. 1637-1642. Spectroscopic studies of die reaction of hexa-cyanoferrate(III) in water and ethanol. 3.3x 10 4 M Fe(NC>3)3 were exposed with a cyanide excess of likewise 3.3x10 mol l"1. With pH values of approximately 10, all the Fe2[Fe(CN)6] was converted into Iron Blue within 48 hours. Cyanate, die anticipated product of die oxidation of die CN-, could not, however, be proven. Perhaps this is further oxidized directly into C02. If this mechanism is assumed, die result, purely stoichiometrically, is that an alkaline environment must be favorable. This finding is supported by die known fact that hexacyan-oferrate(III) is a strong oxidation agent in alkaline medium and is even able to oxidize divalent chrome to hexavalent, therefore, that is, CN ions must have oxidized very quickly J.C. Bailar, Comprehensive Inorganic Chemistry, Vol. 3, Pergamon Press, Oxford 1973, p. 1047. An overly alkaline environment would, however, disturb die complexing of the Fe3+- ion by cyanide, which is then displaced by OH- (Fe(OH)3 then occurs as a by-product) and/or the latter can hardly be displaced from die iron. 

Finally, it should be noted that an overall authoritative account of ligand substitution and complex formation by alkaline and alkaline earth metal ions appeared in Advances in Inorganic Chemistry, Vol. 61. Recently, the need for review and potential modification of some of the basic premises of DFT computations has been discussed.388... 

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