Halide anion binding

In addition to phosphate and halide anion binding, carboxylate chelation by sapphyrin macrocycles has been the subject of recent investigation. To date, two crystal structures have been solved. A 2 1 complex formed between diprotonated sapphyrin 3 and trifluoroacetic acid shows that the oxyanions are chelated above and below the sapphyrin plane (Figure 10). ° Greater complexity of organi-... 

OTHER HALIDE ANION BINDING EXPANDED PORPHYRIN SYSTEMS... 

Scheme 5.46 Synthesis of a peptide 1,1 -ferrocenophane 91, which serves as a host for halide anion binding.

The complexation of anionic species by tetra-bridged phosphorylated cavitands concerns mainly the work of Puddephatt et al. who described the selective complexation of halides by the tetra-copper and tetra-silver complexes of 2 (see Scheme 17). The complexes are size selective hosts for halide anions and it was demonstrated that in the copper complex, iodide is preferred over chloride. Iodide is large enough to bridge the four copper atoms but chloride is too small and can coordinate only to three of them to form the [2-Cu4(yU-Cl)4(yU3-Cl)] complex so that in a mixed iodide-chloride complex, iodide is preferentially encapsulated inside the cavity. In the [2-Ag4(//-Cl)4(yU4-Cl)] silver complex, the larger size of the Ag(I) atom allowed the inner chloride atom to bind with the four silver atoms. The X-ray crystal structure of the complexes revealed that one Y halide ion is encapsulated in the center of the cavity and bound to 3 copper atoms in [2-Cu4(//-Cl)4(//3-Cl)] (Y=C1) [45] or to 4 copper atoms in [2-Cu4(/U-Cl)4(/U4-I)] (Y=I) and to 4 silver atoms in [2-Ag4(/i-Cl)4(/i4-Cl)] [47]. NMR studies in solution of the inclusion process showed that multiple coordination types take place in the supramolecular complexes. 

A majority of the host systems mentioned so far have been shown to encapsulate halide guests as a consequence of the symmetrical nature of their binding pockets, which readily adapt to the spherical symmetry of the halide ion. A study of the bis-tren macrobicyclic ligand 19-6H, however, has revealed that, in addition to accommodating halide anions, it is also able to encapsulate azide, N, within its cylindrical cavity. Solution stability constant measurements indicate that the host... 

A theoretical (AMI molecular orbital) treatment of boron analogues of the katapinand series as well as macrotricyclic compounds related to 16 has also recently appeared. As with the ammonium-based host molecules the macrotricyclic hosts containing four boron atoms exhibited a greater degree of anion specificity as a consequence of the rigidity of their binding sites. In all cases, size selective complexation of halide anions was observed with accompanying decreases in B - B distances and partial sp -> sp rehybridization. ... 

Why do you think corand 4.12 ([24]aneN602) is such an effective ATPase mimic given the discussion of the relatively low affinity for guest species such as alkali metal cations and halide anions set out in Chapters 3 and 4 Similarly, why was a hemispherand chosen as the central cation-binding core of enzyme mimic 12.16 as opposed to a spherand ... 

Receptor 60 possesses similar ion-pair sensing properties to its [Ru(bpy)3]2+ analogue 47 [38]. The neutral receptor naturally showed lower overall stability constants for halides, but the anion binding enhancement observed on the addition of Li+ or Na+ was increased, with a 60-fold enhancement in the stability constant for bromide in the presence of Li+. 

---