Complex labile

The methods of investigation of metal species in natural waters must possess by well dividing ability and high sensitivity and selectivity to determination of several metal forms. The catalytic including chemiluminescent (CL) techniques and anodic stripping voltammetry (ASV) are the most useful to determination of trace metals and their forms. The methods considered ai e characterized by a low detection limits. Moreover, they allow detection of the most toxic form of metals, that is, metal free ions and labile complexes. 

A further factor which must also be taken into consideration from the point of view of the analytical applications of complexes and of complex-formation reactions is the rate of reaction to be analytically useful it is usually required that the reaction be rapid. An important classification of complexes is based upon the rate at which they undergo substitution reactions, and leads to the two groups of labile and inert complexes. The term labile complex is applied to those cases where nucleophilic substitution is complete within the time required for mixing the reagents. Thus, for example, when excess of aqueous ammonia is added to an aqueous solution of copper(II) sulphate, the change in colour from pale to deep blue is instantaneous the rapid replacement of water molecules by ammonia indicates that the Cu(II) ion forms kinetically labile complexes. The term inert is applied to those complexes which undergo slow substitution reactions, i.e. reactions with half-times of the order of hours or even days at room temperature. Thus the Cr(III) ion forms kinetically inert complexes, so that the replacement of water molecules coordinated to Cr(III) by other ligands is a very slow process at room temperature. 

Outer-sphere interactions in solutions of labile complexes. Y. A. Makashev and V. E, Mironov, Russ. Chem. Rev. (Engl. Transl.), 1980, 49, 631-644 (203). 

The most extensively studied family of non-labile complexes is the cobalt(III) ammine series. These are octahedral systems and all those to be considered are low spin <7 systems. The subtle variations that can be achieved synthetically make... 

The related octahedral non-labile complexes which have received some attention will be grouped together simply because there is much less information... 

In the final section of this chapter, we shall attempt to give a brief rationalization of the regularities and peculiarities of the reactions of non-labile complexes which have been discussed in the previous sections. The theoretical framework in which the discussion will be conducted is that of molecular orbital theory (mot). The MOT is to be preferred to alternative approaches for it allows consideration of all of the semi-quantitative results of crystal field theory without sacrifice of interest in the bonding system in the complex. In this enterprise we note the apt remark d Kinetics is like medicine or linguistics, it is interesting, it js useful, but it is too early to expect to understand much of it . The electronic theory of reactivity remains in a fairly primitive state. However, theoretical considerations may not safely be ignored. They have proved a valuable stimulus to incisive experiment. 

There are also examples of induced complex formation, an essential step of which is always an oxidation-reduction reaction. Rich and Taube found that the rate of exchange between PtCl and Cl was considerably increased by addition of cerium(rV). In the presence of this oxidizing agent a labile complex of Pt(III) is formed, the chloride of which is easily exchangeable. Exchange of platinum between PtCl and PtClg is similarly rapid via the intermediate labile PtCIs complex formed by cerium(IV). 

Pt(en)(N03)2] and [Pt(OTf)2L2] (L = mono- or 1/2 bidentate tertiary phosphine) or dinuclear complexes of the type [Pt2(OTf)2(/i-monodentate tertiary phosphine cr-aryl = 4, -biphenyl, / -terphenyL 4,4 -benzophenone, etc.) other structural motifs employing platinum(II) have also been reported.2 0 The addition of bridging, multidentate N-donor ligands of various shapes and sizes to the labile complexes in a suitable solvent system has afforded several classes of discrete, plat-inum(II)-containing polygons, polyhedra, and catenanes. 

Retarders of opposite ionic charge to the dyes can be used [33,36,48-51]. Anionic retarders function by forming a thermally labile complex with the dye and thus lowering the substantivity of the dye for the fibre. Undesirable precipitation of this complex, which is one of the drawbacks of the system, can be inhibited ... 

Bipyridines were efficiently used in supramolecular chemistry [104], Since the molecule is symmetric no directed coupling procedure is possible. In addition, 2,2 6/,2//-terpyridine ligands can lead to several metal complexes, usually bis-complexes having octahedral coordination geometries [105,106], Lifetimes of the metal-polymeric ligand depend to a great extent on the metal ion used. Highly labile complexes as well as inert metal complexes have been reported. The latter case is very important since the complexes can be treated as conventional polymers, while the supramolecular interaction remains present as a dormant switch. 

In a general way, the ions in the first two classes would be considered labile while those in the last two classes would be considered inert. Labile complexes are regarded as those in which the reaction is complete on a time scale that would be comparable to the time necessary to mix the solutions of the reacting species. Such reactions can be studied by flow techniques or by NMR line broadening. Inert complexes are those that can be followed by conventional kinetic techniques. 

Shuman and Michael [326,327] introduced a technique that has sufficient sensitivity for kinetic measurement at very dilute solutions. It combines anodic scanning voltammetry with the rotating-disk electrode and provides a method for measuring kinetic dissociation rates in situ, along with a method for distinguishing labile and non-labile complexes kinetically, consistent with the way they are defined. 

The dimer complex 13 showed, for the first time for kinetically labile complexes, an enhanced activity toward the hydrolysis of the activated... 

The nonlinearity of the system of partial differential equations (51) and (52) poses a serious obstacle to finding an analytical solution. A reported analytical solution for the nonlinear problem of diffusion coupled with complexation kinetics was erroneous [12]. Thus, techniques such as the finite element method [53-55] or appropriate change of variables (applicable in some cases of planar diffusion) [56] should be used to find the numerical solution. One particular case of the nonlinear problem where an analytical solution can be given is the steady-state for fully labile complexes (see Section 3.3). However, there is a reasonable assumption for many relevant cases (e.g. for trace elements such as... 

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