Macrocycles iron complexes

The last example, Figure 15, is a bromo chloro macrocyclic iron complex. Bromine is CIP priority 1, chlorine is 2, the imine nitrogens 3 and 4, the pyridine nitrogen 5, and the amine nitrogens 6 and 7. The complex is pentagonal bipyramidal-seven coordinate, PB-7, the atoms on the axis are priority numbers 12- and the priority numbers for the atom in the plane are given in lowest sequential order, 35476. This clockwise order is symbolized as C. 

Selected other metal ion systems. There have been a number of investigations of the reduction of iron macrocyclic ligand complexes. In one such study, the Fe(n) complex [FeL(CH3CN)2]2+ [where L = (292)] was shown to exhibit three reduction waves in acetonitrile (Rakowski Busch, 1973). Controlled-potential electrolysis at the first reduction plateau (—1.2 V) led to isolation of [FeL]+ for which the esr spectrum is typical of a low-spin Fe(i) system. The quasi-reversible Fe(i)/Fe(n) couple occurs at —0.69 V versus Ag/AgN03. 

It is essential to characterize the reactant species in solution. One of the problems, for example, in interpreting the rate law for oxidation by Ce(IV) or Co(III) arises from the difficulties in characterizing these species in aqueous solution, particularly the extent of formation of hydroxy or polymeric species. We used the catalyzed decomposition of HjOj by an Fe(III) macrocycle as an example of the initial rate approach (Sec. 1.2.1). With certain conditions, the iron complex dimerizes and this would have to be allowed for, since it transpires that the dimer is catalytically inactive. In a different approach, the problems of limited solubility, dimerization and aging of iron(III) and (Il)-hemin in aqueous solution can be avoided by intercalating the porphyrin in a micelle. Kinetic study is then eased. 

C. Che u. C. Poon, Pure Appl. Chem. 60, 1201-1204 (1988) Macrocyclic Amine Complexes of Iron, Ruthenium, and Osmium". 

Simple macrocyclic quadridentate complexes can be synthesized by template reactions from ethers derived from salicylaldehyde and diamines in the presence of appropriate metal ions such as nickel(II) (equation 3).35>36 However, these reactions can also be carried out quite effectively in the absence of metal ions to yield the free ligands, which can be obtained by hydrolysis of the complexes. An iron(II) macrocyclic quinquedentate chelate of this type has been produced by template synthesis (equation 4).37... 

The reaction of 2,6-diacetylpyridine with hydrazine in the presence of iron(II) salts yields a macrocyclic azine complex (equation 34).192 Similar complexes of cobalt(II), zinc(II), magnesium ) and scandium(III) have been prepared more recently.193... 

In the case of the iron complex Fe(OMC) the intensity of the absorption has been related to the existence of stacking phenomena among the macrocyclic units, which are eliminated by interactions with chloride ions or axial ligands [28],... 

Clearly, while porphyrin complexes are obvious candidates for modelling these kinds of biomimetic oxidations, a range of non-heme iron complexes based on macrocyclic and podand ligand have also proved to be successful structural and functional mimics.19 To take one example, Figure 12.13 shows the X-ray structure of the iron (IV) tetramethylcyclam (tmc) oxo complex [Felv(tmc)(0)(MeCN)]2+... 

History. Braun and Tschemak [23] obtained phthalocyanine for the first time in 1907 as a byproduct of the preparation of o-cyanobenzamide from phthalimide and acetic anhydride. However, this discovery was of no special interest at the time. In 1927, de Diesbach and von der Weid prepared CuPc in 23 % yield by treating o-dibromobenzene with copper cyanide in pyridine [24], Instead of the colorless dinitriles, they obtained deep blue CuPc and observed the exceptional stability of their product to sulfuric acid, alkalis, and heat. The third observation of a phthalocyanine was made at Scottish Dyes, in 1929 [25], During the preparation of phthalimide from phthalic anhydride and ammonia in an enamel vessel, a greenish blue impurity appeared. Dunsworth and Drescher carried out a preliminary examination of the compound, which was analyzed as an iron complex. It was formed in a chipped region of the enamel with iron from the vessel. Further experiments yielded FePc, CuPc, and NiPc. It was soon realized that these products could be used as pigments or textile colorants. Linstead et al. at the University of London discovered the structure of phthalocyanines and developed improved synthetic methods for several metal phthalocyanines from 1929 to 1934 [1-11]. The important CuPc could not be protected by a patent, because it had been described earlier in the literature [23], Based on Linstead s work the structure of phthalocyanines was confirmed by several physicochemical measurements [26-32], Methods such as X-ray diffraction or electron microscopy verified the planarity of this macrocyclic system. Properties such as polymorphism, absorption spectra, magnetic and catalytic characteristics, oxidation and reduc-... 

Chanda, A. Popescu, D. L. Tiago de Oliveira, F. Bominaar, E. L. Ryabov, A. D. Miinck, E. Collins, T. J. High-valent iron complexes with tetraamido macrocyclic ligands ... 

Effect of Pressure on Proton-Coupled Electron Transfer Reactions of Seven-Coordinate Iron Complexes in Aqueous Solution It has been shown that seven-coordinate Fe(III) diaqua complexes consisting of a pentaaza macrocyclic ligand possess superoxide dismutase (SOD) activity, and therefore could serve an imitative SOD function.360 Choosing appropriate chemical composition of a chelate system yielded suitable pKa values for the two coordinated water molecules so that the Fe(III) complexes of 2,6-diacetylpyridine-bis(semicarbazone) (dapsox) and 2,6-diacetylpyridine-bis(semioxamazide) (dapsc) (see Scheme 7.12) would be present principally in the highly active aqua-hydroxo form in solution at physiological pH.361... 

Nearly all iron complexes of synthetic macrocyclic ligands contain nitrogen either as the only ligand atom or as the major donor present. Moreover, most macrocyclic ligands are tetradentate usually presenting a roughly planar N4 donor set to the centrally complexed metal ion. The comprehensive review by Melson390 of the coordination chemistry of macrocyclic compounds should be consulted for work published up until 1978. 

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