Coordination spheres substitution

As an example, consider reaction (6.1). Here, the Cu2+aq ion has water ligands in its coordination sphere substituted by a stronger ligand, in this case ammonia, to form [Cu(NH3)4]2+. Multiple ligand substitution is assisted by the use of an excess of the incoming ligand to drive equilibria towards the fully-substituted compound. 

Divalent molybdenum compounds occur in mononuclear, dinuclear, and hexanuclear forms. Selected examples are shown in Figure 6. The mononuclear compounds are mostiy in the realm of organometaUic chemistry (30—32). Seven-coordinate complexes are common and include MoX2(CO)2(PR3)2, where X = Cl, Br, and I, and R = alkyl MoCl2(P(CH3)3)4, heptakis(isonitrile) complexes of the form Mo(CNR) 2 (Fig. 6d), and their chloro-substituted derivatives, eg, Mo(CNR)3CR. The latter undergo reductive coupling to form C—C bonds in the molybdenum coordination sphere (33). 

Outer-sphere. Here, electron transfer from one reactant to the other is effected without changing the coordination sphere of either. This is likely to be the ea.se if both reactants are coordinatively. saturated and can safely be assumed to be so if the rate of the redox process is faster than the rates observed for substitution (ligand tran.sfer) reactions of the species in question. A good example is the reaction. 

Two commonly used synthetic methodologies for the synthesis of transition metal complexes with substituted cyclopentadienyl ligands are important. One is based on the functionalization at the ring periphery of Cp or Cp metal complexes and the other consists of the classical reaction of a suitable substituted cyclopentadienyl anion equivalent and a transition metal halide or carbonyl complex. However, a third strategy of creating a specifically substituted cyclopentadienyl ligand from smaller carbon units such as alkylidynes and alkynes within the coordination sphere is emerging and will probably find wider application [22]. 

This is an example of a substitution reaction, a reaction in which one 1 ewis base takes the place of another. Here the CN ions drive out H20 molecules from the coordination sphere of the [Fe(H20)6]2+ complex and take their place. Replacement is less complete when certain other ions, such as Cl, are added to an iron(II) solution ... 

In the skeleton of many chelating diphosphines, the phosphorus atoms bear two aryl substituents, not least because the traditional route to this class of compounds involves the nucleophilic substitution with alkali metal diarylphosphides of enantiopure ditosylates derived from optically active natural precursors, approach which is inapplicable to the preparation of P-alkylated analogs. The correct orientation of these aryl substituents in the coordination sphere has been identified as a stereo chemically important feature contributing to the recognition ability of the metal complex [11,18-20]. 

Hydroarylation, (addition of H-Ar, Ar = aryl), of alkynes, catalysed by Pd(OOCCH3)2 or Pd(OOCCFj)j in acetic acid, is an atom-economic reaction, giving rise to substituted c/i-stilbenes (Fujiwara reaction). Catalytic conversions and improved chemoselectivity to the mono-coupled product under mild conditions can be achieved by modification of the metal coordination sphere with NHC ligands. Hydroarylation of mesitylene by ethylpropiolate (Scheme 2.19) catalysed by complex 107 (Fig. 2.18) proceeds in good conversions (80-99%, 1 mol%) under mild conditions at room temperature. 

Fig. 1. Mean lifetimes of a single water molecule in the first coordination sphere of a given metal ion, th2o> and the corresponding water exchange rate constants, h2o- The tall bars indicate directly determined values, and the short bars indicate values deduced from ligand substitution studies. References to the plotted values appear in the text.

The replacement of five waters in [Cr(H20)6]3+ by NH3 in [Cr(NH3)5H20]3+ causes a 20-fold increase in the lability of the single remaining water (which is quite small by comparison with such replacement in [Ni(H20)6]2 +, as seen from Table V) and appears to decrease the importance of the a-activation mode in the approach to the transition state (see Section III,G). Assuming that the free radii (222) of H20 (138 pm) and NH3 (169 pm) reflect their relative electrostricted coordinated radii, it is anticipated that the first coordination sphere of [Cr(H20)6]3+ will be less crowded than that of [Cr(NH3)5H20]3+ and that the extent of a-activation character in the substitution of water in the latter species will decrease. 

The introduction of redox activity through a Co11 center in place of redox-inactive Zn11 can be revealing. Carboxypeptidase B (another Zn enzyme) and its Co-substituted derivative were oxidized by the active-site-selective m-chloroperbenzoic acid.1209 In the Co-substituted oxidized (Co111) enzyme there was a decrease in both the peptidase and the esterase activities, whereas in the zinc enzyme only the peptidase activity decreased. Oxidation of the native enzyme resulted in modification of a methionine residue instead. These studies indicate that the two metal ions impose different structural and functional properties on the active site, leading to differing reactivities of specific amino acid residues. Replacement of zinc(II) in the methyltransferase enzyme MT2-A by cobalt(II) yields an enzyme with enhanced activity, where spectroscopy also indicates coordination by two thiolates and two histidines, supported by EXAFS analysis of the zinc coordination sphere.1210... 

Varying ratios of the ligands 7V-(2-thiophenyl)-2,5-dimethylpyrrole and V-methylimidazole were used to form tetrahedral zinc complexes with S4, S3N, and S2N2 coordination spheres. X-ray structural analyses and IR spectra were recorded for all compounds and the relevance to zinc finger proteins was discussed. The comparison to cobalt and cadmium structures showed only minor differences, supporting the theory that changes on substituting these metals into zinc proteins would be minor.538... 

Tc2[(CH3)3CCOO]4 C12. The first binuclear d4-d4 technetium complex was obtained by Cotton and Gage [45] by oxidative substitution of the chloride ions in the coordination sphere of [Tc2Cl8]3 by trimethylacetate ions. The substitu-... 

From the viewpoint of coordination chemistry, a substitution reaction can be defined as a process whereby a ligand in a complex is replaced by another ligand from outside the coordination sphere [1], Substitution reactions by metal complexes have been classified by Saito [2] according to Taube s definition [3] of inertness. Saito classified metal ions into three groups as follows ... 

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