Phthalocyanine iron II

Additional axial ligands can be linked to the center of phthalocyanines either by valence bonds as in the case of silicium phthalocyanine151 or by coordinative bonds as in the case of bis(pyridino)iron(II) phthalocyanine [PcFe(py)2].131353... 

An experimental procedure for the conversion of iron(II) phthalocyanine into lithium methyl-(phthalocyanine)ferrate(II) can be found in Houben-Weyl, Vol. 13/9a, p 228. For analogous reactions involving cobalt, see Houben-Weyl, Vol. 13/9b, pp 55, 87. 

Kimer JF, Dow W, Scheldt WR. 1976. Molecular stereochemistry of two intermediate-spin complexes. Iron(II) phthalocyanine and manganese(II) phthalocyanine. Inorg Chem 15 1685-1690. 

Iron phosphate glasses, 12 585, 616 Iron phosphates, 18 839 Iron phosphating, 16 214-215 applications for, 16 215 Iron phthalocyanine, isolation of, 24 36 Iron(II) phthalocyanine, 14 547 Iron plating baths, 9 814t Iron porphyrin-catalyzed dye oxidation, 9 383-384... 

The structure of bis(piperidine)-aPy5-tetraphenylporphinatoiron(ii) shows the complex to have an octahedral [FeN ] core. The 4 1 complex between 4-methylpyridine and iron(ii) phthalocyanine has only two 4-Mepy groups co-ordinated to the metal in a rrfl/j.< -octahedral arrangement.The dimerization of iron(ii) phthalocyanine in DM SO has been studied and iron(ii) phthalocyanines have been used as n.m.r. shift reagents for amines. Although... 

Investigations continue of ligand replacement reactions of the two coordinated solvent molecules of iron(II) phthalocyanine, (154), in It has been confirmed that both steps can be... 

An equilibrium and kinetic study of the iron(II) phthalocyanine/nitric oxide system in DMSO, at 293 K, showed that formation of [Fe(pc)(NO)] obeys a simple second-order rate law, like [Fe(pc)] plus CO but unlike [Fe(pc)] plus dioxygen. A rate constant for dissociation of [Fe(pc)(NO)] was derived from its formation rate and equilibrium constants. " ... 

Unlike the metal atoms in the chalcogenides discussed in the previous section, the iron atoms in iron(II) tetraphenyl porphyrins and the related iron(II) phthalocyanine generally occupy crystallographic sites with symmetry T or 1 only. The exception is the iron site in iron(II) tetraphenyl porphyrin (FeTPP), space group I42d, which has 4 symmetry. 

In solution the photochromism of coordination compounds can result from photoinduced isomerization (e.g. metal dithizonates186-188), substitution (e.g. iron(II) phthalocyanine in the presence of benzyl isocyanide189) and oxidation—reduction (e.g. tris(diethyldithiocarbamato)-nickel(IV) bromide190). 

Depending on the type of iron catalyst, the reaction seems to take different mechanistic pathways. According to Johannsen and Jorgensen s results, the catalytic cycle starts with the formation of nitrosobenzene 32 either by disproportionation of hydroxylamine 29a to 32 and aniline in the presence of oxo iron(IV) phthalocyanine (PcFe4+=0) or by oxidation of 29a [131]. The second step, a hetero-ene reaction between the alkene 1 and nitrosobenzene 32, yields the allylic hydroxylamine 33, which is subsequently reduced by iron(II) phthalocyanine to afford the desired allylic amine 30 with regeneration of oxo iron(IV) phthalocyanine (Scheme 3.36). That means the nitrogen transfer proceeds as an off-metal reaction. The other byproduct, azoxybenzene, is probably formed by reaction of 29a with nitrosobenzene 32. 

With Z = 2, the iron(II) phthalocyanine molecule occupies a 1 site, and its molecular and crystal stmctures are shown in Fig. 9.6.6. 

Table 22 Mossbauer Parameters for Iron(II) Phthalocyanine and Selected Derivatives at Room and Liquid Nitrogen Temperatures...

Models which allow interpretation of X-ray diffraction data in terms of orbital populations, radial dependence of the orbitals and LCAO coefficients are discussed. They are applied to experimental data on iron(II) phthalocyanine, iron(II) meso-tetraphenylporphyrin and its bis-pyridyl and bis-tetrahydrofurane derivatives. The diffraction studies indicate that the first two complexes are intermediate spin complexes with differing ground states while the last two are respectively low- and high-spin iron(II) compounds. A difference between the two intermediate spin complexes is thought to be related to the effect of the crystalline environment. This interpretation implies that the leading contributor to the ground... 

The iron(II) phthalocyanine complexes [FePc]" ( = —1, 0, +1, 2, 3, 4) have been studied over a range of temperature, and the observed spectra discussed in terms of the molecular orbital treatment of these complexes [23]. Progressive reduction has Uttle effect on the spectrum. 

In 1932, a dark blue by-product was isolated during the industrial production of phthalimide from phthalic anhydride and ammonia in an iron vessel. This unexpected by-product was eventually identified as iron(II)phthalocyanine Now we know that the iron had templated the formation of this macrocycle [8]. Curtis investigated the condensation of acetone 4 and 1,2-diaminoethane 3 in the presence of metal cations and showed that the macrocycles 5 and 6 could be prepared both by templated and untemplated processes (Scheme 1-2) [9, 10],... 

The dioxygen ligand is said to be stabilized by the presence of strong (T-donors in the trans position. Such complexes are of specific interest as models of the active myoglobin center (473). Preliminary reports of a related copper(II) system have appeared (286). Studies on the effect of extraplanar Me SO coordination on phthalocyanine derivatives of cobalt (109) and iron (315-317) have been performed and show that, for example, the low-spin d iron(II) phthalocyanine complex dissolves in Me SO to give a diamagnetic blue solution which may be reacted further with donors such as imidazole, effecting replacement at the axial sites (62). 

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