Picket fence complexes

Figure 9 A few schematic examples of mononuclear Fe(II) -porphyrin derivatives used to prevent the irreversible oxidation to oxygen-bridged binuclear Fe(III) derivatives. (a) Picket-fence complexes (b) strapped complexes (c) capped complexes (d) picnic-basket complexes (e) pocket complexes...

Particularly important in affirming this kind of investigation has been the Collman s picket-fence complex illustrated in Figure 10a, in that the molecular structure of its oxygenated form has been solved, Figure 10b.14... 

Figure 10 (a) Colmann s picket-fence complex (b) X-ray structure of the corresponding... 

Oxygen transport has received considerable attention. "Picket fence" cobalt porphyrin complexes are selectively blocked at the hindered face so that imidazole bases may only coordinate from the open side. As seen in Scheme 11, the imidazole-coordinated picket fence complex has a vacant coordination site at the top. The small linear oxygen molecule can traverse the "fence" to coordinate reversibly with cobalt from the top side. By dispersing such complexes in films one can build membranes which facilitate oxygen transport. This type of chemistry is one approach to making artificial blood. 

This review is particularly concerned with the bonding modes of the dioxygen ligand, and the factors affecting which of the various possible orientations it assumes in any particular complex. We shall therefore consider all previous work, from the earliest work on synthetic oxygen carriers, right up to the most recent studies on picket-fence and other synthetic porphyrins. All work concerned with an irreversible system will illustrate some principle appertaining to reversibility. On this basis we shall then attempt to provide a unified rationale for ... 

The first test case was the ferrous high-spin state (Fe, S = 2) in the picket-fence porphyrin acetate complex [Fe(CH3COO)(TPpivP)] [13, 23], which is a model for the prosthetic group termed P460 of the multiheme enzyme hydroxyl-amine oxidoreductase from the bacterium Nitrosomonas europeae. Both the picket-fence porphyrin and the protein P460 exhibit an extraordinarily large quadrupole splitting, as observed by conventional Mossbauer studies [56]. 

Fig. 9.21 NFS spectra of the paramagnetic picket-fence porphyrin complex [ Fe(CH3COO) (TPpivP)] obtained at 3.3 K in a field of 6.0 T applied (a) perpendicular to both the synchrotron beam and the polarization vector of the radiation and (b) perpendicular to the synchrotron beam but parallel to the polarization vector of the radiation. The solid lines are simulations with the SYNFOS program using 5 = 2 and parameters described in the text. (Taken from [13])...

The NIS investigation of heme complexes includes various forms of porphyrins (deuteroporphyrin IX, mesoporphyrin IX, protoporphyrin IX, tetraphenylpor-phyrin, octaethylporphyrin, and picket fence porphyrin) and their nitrosyl (NO) and carbonyl (CO) derivatives, and they have been the subject of a review provided by Scheidt et al. [109]. 

The picket fence Ni11 complex [Ni(TpivPP)] ((70) TpivPP meso-a-a-a-a-lclrakis-(o-pivalamidophenyl)porphyrin) is reversibly oxidized by three electrons in two steps and generates as final product [Ni(Tipw)]3+ which was characterized as a Nilv cation radical in solution by both UV-visible and EPR spectroscopy.289... 

Other studies have been based on synthetic systems incorporating haem moieties (Baldwin Perlmutter, 1984). One elegant study of this type involves the Fe(n) complex of the picket fence ligand (313)... 

In order to prepare and isolate solid-state, crystalline, oxygenated iron-heme model complexes, chemists learned to synthesize (by self-assembly methods) and oxygenate many types of hindered porphyrins. For instance, capped porphyrins were synthesized by direct condensation of a suitable tetraaldehyde with four pyrrole molecules.37 Picket-fence porphyrins such as I e(TPP)((V-MeIm) (where TPP = meso-tetraphenylporphyrin and /V-Melm = (V-methylimidazole)... 

Synthetic models of myoglobin and hemoglobin are complex molecules that mimic the stereochemical properties of the protein active center [24] and have oxygen affinities similar to those measured for the protein [25-27]. The first heme model that reversibly binds oxygen (i.e. the picket-fence-oxygen complex Fe(TpivPP)(l,2-Melm)(02), shown in Fig. 3.3) was obtained in the early nine-teen-seventies by Collman and coworkers (TpivPP = tetrapivalami-nophenyl porphyrin 2-meIm = 2-methylimidazole) [18]. Research on synthetic models of the protein has led to a deeper understand-... 

The Picket-fence-oxygen Biomimetic Complex 3.3.2.1 Interplay Structure/Electronic State... 

In this first part of this section, complexes are grouped according to the axial ligands. We then move to pocket and picket-fence porphyrins and finally focus on multinuclear species. 

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