Imidazolate ligands

FIGURE 21.18 (a) The Cn site of cytochrome oxidase. Copper ligands inclnde two histidine imidazole groups and two cysteine side chains from the protein, (b) The coordination of histidine imidazole ligands to the iron atom in the heme a center of cytochrome oxidase. 

Several model systems related to metalloenzymes such as carboxypeptidase and carbonic anhydrase have been reviewed. Breslow contributed a great deal to this field. He showed how to design precise geometries of bis- or trisimidazole derivatives as in natural enzymes. He was able to synthesize a modified cyclodextrin having both a catalytic metal ion moiety and a substrate binding cavity (26). Murakami prepared a novel macrocyclic bisimidazole compound which has also a substrate binding cavity and imidazole ligands for metal ion complexation. Yet the catalytic activities of these model systems are by no means enzymic. 

More recently 233) it has been reported that cross-linked polystyrene containing imidazole ligands did not provide a support rigid enough to prevent dimerization, and that the p-oxo dimer was benzene extracted from oxygenated tetraphenyl porphyrin iron(ll), Fe(TPP), which had been attached to the modified polystyrene. A discussion of model synthetic porphyrins, from which definitive structural and other physical data are obtained, is given in section V.C. 

A number of further thioether-imidazole ligands with NS, N2S, N2S2, and N4S2 donor set have been characterized by X-ray crystallography, and they show a comparable coordination behavior.1322-1328... 

Novel cationic methyl and neutral methyl, chloro Pd11 complexes have been synthesized with various functionalized imidazole ligands. For the first time, structurally characterized examples of this type of Pd complex could be obtained. The chelate ligand is shown to adopt a boat conformation. Inversion of the chelate ring was established by NMR spectroscopy. Depending on electronic and steric features of the ligand, the complexes can act as catalysts in the CO/ethylene as well as the Fleck reaction.186... 

Heptanuclear Trigonal Prismatic Clusters Stabilized by Monodentate Imidazole Ligand... 

Figure 3.4 shows the models used in the calculations of the active center. They are of the type FeP-AB (FeP = iron-porphyrin, AB = CO, NO, 02), Heme-AB (AB = CO, NO, 02), and FeP(Im)-AB (Im=imidazole). The axial imidazole ligand mimics the effect of the proximal histidine amino acid (Fig. 3.2). 

Pei and coworkers [362] synthesized fluorene copolymer functionalized with imidazole ligands in the side chains (270). The PL emission of 270 was sensitive to the presence of metal cations in solution (particularly efficient quenching was due to Cu2+), which makes it a promising material for fluorescent chemosensing. 

Another notable example of the anomalous behavior of imidazole ligands is the kinetic tram effect observed for the rates of substitution of 02 for CO in the hemes Fe(TPP)02L ([29], M = Fe, X = 02, L = Py, Pip, or l-Melm) according to Eq.(4)and Table 8 30). One of the three nitrogen donors in question, l-Melm, stabilizes the dioxygen adduct in a manner not to be expected from its basicity. The substitution is clearly of the SN1 type, the elimination of the 02 molecule being the rate-determining step. 

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