Iron acetylacetonate complexes

Iron, tris(hexafluoroacetylacetone)-structure, 1,65 Iron, tris(oxalato)-chemical actinometer, 1,409 photoreduction, 1,471 relief-image-forming systems, 6,125 Iron, tris(l,10-phenanthroline)-absorptiometry, 1,549 racemization, 1,466 solid state, 1,467 structure, 1, 64 lron(III) chloride amino acid formation prebiotic systems, 6,871 Iron complexes acetonitrile. 4,1210 acetylacetone, 2,371 amidines... 

Figure 1 Transfer chemical potentials for selected iron complexes from water into aqueous methanol (on the molar scale, at 298 K). Ligand abbreviations not appearing in the list at the end of this chapter are acac = acetylacetonate (2,4-pentanedionate) dmpp = l,2-dimethyl-3-hydroxy-4-pyridinonate, the anion from (24) malt = maltolate (2-methyl-3-hydroxy-4-pyranonate, the anion from (233)).

The results published thereafter by Kochi s group are especially interesting from a mechanistic point of view . Indeed, for preparative chemistry the yields are not satisfactory and the reaction is limited to reactive alkenyl bromides such as propenyl and styryl bromides (Table 4). Neumann and Kochi were the first to replace iron(III) chloride by iron(III) acetylacetonate or related complexes such as Fe(dbm)3 (iron tris-dibenzoylmethanato) that are less hygroscopic and easier to handle. 

Probably substitution of the cyclopentadienyl ligand on alcoholysis and hydrolysis, and its transfer in reactions of di- and monocyclopentadienyl-titanium derivatives with FeClj or iron(II) acetylacetonate, follows a mechanism common for 77-ligand exchange in other metal 77-complexes (see later). 

In the case of catalysis by iron complexes with HMPA, which does not transformed in the course of oxidation, it is possible to estimate the apparent activation energies for micro steps of ethylbenzene oxidation - chain initiation (activation by O2) and propagation (Cat + R02 ) at two temperatures, 80 and 120°C. These are EJ w =24.53 and 13.03 kcal/mol and (Wp ) =21.46 and 17.63 kcal/mol in the absence and presence of HMPA, respectively. The gain in activation energy of the initiation reaction 11.5 kcal/mol via the coordination of HMPA is approximately equal to the energy 10 kcal/mol of ligand addition to metal acetylacetonates [139]. The difference in between the initiation and propagation reactions in the presence of HMPA is presumably responsible for tendency of oxidation selectivity to increase with decrease in temperature. 

Biosensitisers and photosensitisers are nsed to obtain PE with predictable life times. Iron complexes Fe(iii)-acetylacetonate, Fe(iii)-2-hydroxy-methylacetophenoneoxime, transition metal (Co, Ni, Cr, Zn)-N,N -diethyldiselenocarbamates or other metallic complexes, and blends with natural polymers (starch, cellulose, lignin, proteins) are mostly used. 

In the effect of iron (II) acetylacetonate complexes one can find an analogy with the action of Fe -ARD or Fe -acetylacetone Dioxygenase (Dkel) (Scheme 5.2). ... 

In chelation complexes (sometimes called inner complexes when uncharged) the central metal ion coordinates with a polyfunctional organic base to form a stable ring compound, e.g. copper(II) acetylacetonate or iron(III) cupferrate ... 

The acetylacetonates are stable in air and readily soluble in organic solvents. From this standpoint, they have the advantage over the alkyls and other alkoxides, which, with the exception of the iron alkoxides, are not as easily soluble. They can be readily synthesized in the laboratory. Many are used extensively as catalysts and are readily available. They are also used in CVD in the deposition of metals such as iridium, scandium and rhenium and of compounds, such as the yttrium-barium-copper oxide complexes, used as superconductors. 1 1 PI Commercially available acetyl-acetonates are shown in Table 4.2. 

In the early work on the thermolysis of metal complexes for the synthesis of metal nanoparticles, the precursor carbonyl complex of transition metals, e.g., Co2(CO)8, in organic solvent functions as a metal source of nanoparticles and thermally decomposes in the presence of various polymers to afford polymer-protected metal nanoparticles under relatively mild conditions [1-3]. Particle sizes depend on the kind of polymers, ranging from 5 to >100 nm. The particle size distribution sometimes became wide. Other cobalt, iron [4], nickel [5], rhodium, iridium, rutheniuim, osmium, palladium, and platinum nanoparticles stabilized by polymers have been prepared by similar thermolysis procedures. Besides carbonyl complexes, palladium acetate, palladium acetylacetonate, and platinum acetylac-etonate were also used as a precursor complex in organic solvents like methyl-wo-butylketone [6-9]. These results proposed facile preparative method of metal nanoparticles. However, it may be considered that the size-regulated preparation of metal nanoparticles by thermolysis procedure should be conducted under the limited condition. 

Other methods reported for the determination of beryllium include UV-visible spectrophotometry [80,81,83], gas chromatography (GC) [82], flame atomic absorption spectrometry (AAS) [84-88] and graphite furnace (GF) AAS [89-96]. The ligand acetylacetone (acac) reacts with beryllium to form a beryllium-acac complex, and has been extensively used as an extracting reagent of beryllium. Indeed, the solvent extraction of beryllium as the acety-lacetonate complex in the presence of EDTA has been used as a pretreatment method prior to atomic absorption spectrometry [85-87]. Less than 1 p,g of beryllium can be separated from milligram levels of iron, aluminium, chromium, zinc, copper, manganese, silver, selenium, and uranium by this method. See also Sect. 5.74.9. 

Takacs has reported the cyclization of tu-enedienes catalyzed by an iron(0) complex that is generated in situ through the reduction of iron(m) tris(acetylacetonate) with triethylaluminum in the presence of a ligand such as 2,2 -bipyridine or bisoxazoline (Scheme 100). The 1,4-diene cycloadducts are obtained in very good yields.366... 

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