Phthalocyanine iron with

The reduced alkyl complexes are reoxidized by O2 to the iron(lll) alkyls. The corresponding diamagnetic phthalocyanine iron(ll) alkyl complexes, rFe(Pc)R), were prepared by two-electron reduction of Fe(Pc) by LiAIFl4 to give [Fe(Pc) (actually the Fe(I) phthalocyanine radical anion) followed by reaction with Mel, Etl or i-PrBr. The methyl compound, [Fe(Pc)CHi] was characterized by X-ray crystallography. ... 

Finally, phthalocyanine iron catalysts were also used for the oxidation of alcohols to yield corresponding carbonyl compounds with nonbenign hypervalent iodine oxidants [147]. 

In 1929, Linsted obtained samples of this complex from ICI chemists (Scottish Dyes Ltd was now owned by ICI). ICI had developed two routes leading to the phthalocyanine iron complex. One method started from phthalic anhydride, iron, and ammonia, while the second pathway proceeded from phthalimide, iron sulfide, and ammonia. In 1933/34, elucidation of the phthalocyanine structure was credited to Linstead. The corresponding copper and nickel phthalocyanines had been prepared in the meantime. ICI introduced the first Copper Phthalocyanine Blue to the market as early as 1935, and the Ludwigshafen subsidiary of the IG Farben-industrie followed suit with a corresponding product. 

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... 

Monteverde Videla AHA, Osmieri L, Armandi M, Specchia S (2015) Varying the morphology of Fe-N-C electrocatalysts by templating iron phthalocyanine precursor with different porous Si02 to promote the oxygen reduction reaction. Electrochim Acta 177 43-50... 

Nabae et al. [124] pyrolyzed iron phthalocyanine mixed with phenolic resin (FePc/PhR) in inert gas at different temperatures, each for five hours, and found best catalytic activity toward ORR at 600°C. A comparison to metal-free H2PC/PI1R reference samples, as shown in Fig. 16.10 (a H2Pc/PhR, b FePc/PhR), evidenced significant higher current densities and higher onset potentials for the samples prepared with iron phthalocyanine. 

LB multilayer thin films can also be formed from nickel-tetra-tert-butyl-phthalocyanine, iron-tetra-tert-butylphthalocyanine, and mixtures of these phthalocyanines with PHT. The phthalocyanine molecules serve as both a surface active agent to promote spreading and an electroactive material [424,425]. 

Hu X, Xia D, Zhang L, Zhang J (2013) High crystalUnity binuclear iron phthalocyanine catalyst with enhantxxl ptaformance for oxygen reduction reaiaion. J Power Sour 231 91-96... 

Air oxidation of dyestuff waste streams has been accompHshed using cobalt phthalocyanine sulfonate catalysts (176). Aluminum has been colored with copper phthalocyanine sulfonate (177,178). Iron phthalocyanine can be used as a drier in wood oil and linseed oil paints (179). 

Phthalocyanines are excellent lubricants at temperatures of 149—343°C (191). Combinations with other lubricants, like grease, molybdenum, or tungsten sulfides, have found appHcations in the automotive industry or professional drilling equipment (192—195). Further uses include indicators for iron(Il), molybdenum(V), and uranium(IV) (196) or redox reactions (197), medical appHcations like hemoglobin replacements (198) or sterilisation indicators (199), or uses like in gas filters for the removal of nitrogen oxides from cigarette smoke (200). 

Chromium(II) phthalocyanine (PcCr) is prepared from phthalonitrile and hexacarbonylchro-mium(O) in 1-chlornaphthalene.234 PcCr(OAc) is prepared from phthalonitrile and chro-mium(III) acetate without solvent235 or in nitrobenzene starting from chromium(II) acetate236 under reflux. Chromium(lll) phthalocyanine also forms /t-oxo dimeric complexes,237 which are more common with iron phthalocyanines. 

In addition to nonheme iron complexes also heme systems are able to catalyze the oxidation of benzene. For example, porphyrin-like phthalocyanine structures were employed to benzene oxidation (see also alkane hydroxylation) [129], Mechanistic investigations of this t3 pe of reactions were carried out amongst others by Nam and coworkers resulting in similar conclusions like in the nonheme case [130], More recently, Sorokin reported a remarkable biological aromatic oxidation, which occurred via formation of benzene oxide and involves an NIH shift. Here, phenol is obtained with a TON of 11 at r.t. with 0.24 mol% of the catalyst. 

Previous studies by Sorokin with iron phthalocyanine catalysts made use of oxone in the oxidation of 2,3,6-trimethylphenol [134]. Here, 4 equiv. KHSO5 were necessary to achieve full conversion. Otherwise, a hexamethyl-biphenol is observed as minor side-product. Covalently supported iron phthalocyanine complexes also showed activity in the oxidation of phenols bearing functional groups (alcohols, double bonds, benzylic, and allylic positions) [135]. Besides, silica-supported iron phthalocyanine catalysts were reported in the synthesis of menadione [136]. 

A variety of aUcenes can be converted to aziridines with PhINTs in good yields (48-90%) using iron phthalocyanine as catalyst (Scheme 24) [79]. It is noteworthy... 

Iron phthalocyanine is an efficient catalyst for intermolecular amination of saturated C-H bonds. With 1 mol% iron phthalocyanine and 1.5 equiv. PhlNTs, amination of benzylic, tertiary, and ally lie C-H bond have been achieved in good yields (Scheme 31). With cyclohexene as substrate, the allylic C-H bond amination product was obtained in 75% yield, and the aziridination product was found in minor amount (17% yield) [79]. 

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