Group 13 elements cationic complexes

The more stable the metal complex, the lower the pH at which it can be quantitatively formed. Elements in the first group may be titrated with EDTA at pH 1 to 3 without interference from cations of the last two groups, while cations of the second group may be titrated at pH 4 to 5 without interference from the alkaline earths. 

Uniformly, within this group of cations, perchlorate ion accompanying the transition-element cation is replaced by nitrate (7,31), thiocyanate (7,52), or halide (7,6). Nitrate is probably replaced by thiocyanate, but a secondary change takes place in many systems, which makes direct comparison difficult (see below). If one then makes the further reasonable assumption that solvent interference can be used as an inverse measure of tendency to bind to the central metal cations, thiocyanate, whose competition with alcohol is less efficient (52) than that of chloride (6), should be somewhat replaceable with chloride. Comparisons between chloride and thiocyanate in acetonitrile show also that the formation of a complex with a given anion/cation ratio takes place much more readily with chloride than with thiocyanate (55, 34). By the same criterion, from experiments in alcoholic solution (55), bromide should replace chloride, and an extrapolation of the behavior to iodide seems reasonable. 

A wide variety of cyclopropenylium metal cations has been prepared and studied over the past two decades, ranging from main group elements (Li, Mg) through transition metal -complexes (Fe, Mn, Pd, Pt). Extensive NMR studies suggest that the metal carbene... 

Figure 6.4. Hydrolysis of metal ions, (a) Predominant pH range for the occurrence of aquo, hydroxo, hydroxo-oxo, and 0x0 complexes for various oxidation states. The scheme attempts to show a useful generalization, but many elements cannot be properly placed in this simplified diagram because other factors, such as radius and those related to electron distribution, have to be considered in inteipreting the acidity of metal ions, (b) The linear dependence of the log,o of the first hydrolysis constant Ki = MOH H / M on the ratio of the charge to the M-O distance (z/d) for four groups of cations (25°C). (Note change of abcissa zero for different groups.) (From Baes and Mesmer, 1976.) (c) Hydrolysis constants of some important metal ions.

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