Chelation ring size

Experimental studies show that chelating spectator ligands impart a degree of stability to complexes of type 23 (Scheme 13.10) [42]. If monodentate phosphine ligands are used decomposition is rapid at 20°C, however, using dppp no decomposition is detected after 24 h [19]. It was found that the rate of decomposition could be linked to the chelate ring size at 65°C, with dppp decomposition was complete after 6 h, with dppe only a small amount of decomposition occurred after this time [42]. 

Effect of Chelate Ring Size on Complex Stability Comparison of Stabilities of Complexes of EDTA (Chelate Ring Size Five Involving the Two Nitrogens) and TMDTA (Analogous Chelate Ring Size Six ) ... 

The chelate ring size principle can have structural effects as well as effects on thermodynamic stability in aqueous solution. An example is coordination of metal ions by sugars (44). The cyclic polyol cts-inositol can coordinate metal ions in two distinct ways (Fig. 14) (45). In ax-ax-ax bonding (Fig. 14), the metal ion is part of three fused six-membered chelate rings. Alternatively, in ax-eq-ax coordination, the metal ion is part of two fused five-membered and one six-membered chelate rings. Angyal has noted that metal ions of radius more than 0.8 A adopt the ax-eq-ax structure (44), whereas with an ionic radius... 

Effect of Chelate Ring Size on Complex Stability with Metal Ions of Different Sizes Oxalate (Ring Size Five) and Malonate (Ring Size Six)°... 

The effect of /rfive-coordinate aluminum alkyls have been discussed.94 Studies have also focused on the equilibrium between four-coordinate and five-coordinate isomers in compounds of the type [R2Al /i-0(GH2) ER1x ]2 (n = Z, 3 ER1x = OR1, SR1, NRX2) (shown in Figure 7(h) for n = Z). Factors that control this equilibrium and hence the coordination around the aluminum include the steric bulk of the substitutent at the aluminum (R), and the Lewis base donor R1, the basicity of the neutral donor group ER1, and the chelate ring size (as determined by n).95... 

Chelate ring size Acidic groups Coordinating atoms Compound group and examples... 

Formation of metal-organic chelate complexes results in stronger complexation (i.e., larger values) compared to interaction with monodentate ligands (Chapter 3). The common types of bidentate ligands are presented in Table 4.9 the chemistry of these complexes has been extensively discussed in the literature [14,47], Chapter 3 presents the most important factors in the formation of such complexes (1) the type of binding atom (2) the chelate ring size (or bite ) ... 

Table 4.16 Consultants for Extraction of Actinide Amides from Nitrate Solutions into an Organic Solvent Showing the Effect of Chelate Ring Size...

Similar, but more extensive, studies of the co-ordination behaviour of the bifunctional ligands (70a) and (70b) with a range of metals have revealed both P,N and P,P bonding. For the Pd" complexes [PdXjL] (X = Cl, Br, or I), i.r. data indicate that both ligands employ P,P co-ordination. The choice of donor atom is discussed in terms of chelate ring size and stereochemical preferences of the various metals. "... 

Lewis acid-base interactions, 42 89-143 change of HSAB behavior, 42 104 chelate ring size and metal ion selectivity, 42 109-118... 

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