Nitration copper acetylacetonate

The unusual copper nitrate-acetic anhydride reagent reacted with acetyl-acetone itself to form bis-(3-nitro-2,4-pentanediono) copper(II) (V), the same compound prepared by Nyholm (18). A novel elaboration of this reaction was treatment of hydrated chromium (III) nitrate with acetylacetone in acetic anhydride to yield a mixture of mono- and dinitrochromiumacetylacetonate (XI and XII). 

In some preliminary studies on the eflFect of the metallic anion a series of reactions was run in which chloride in both the palladium and copper salts was replaced by other anions. When acetate was used, results similar to the chloride systems were obtained although product distribution was somewhat different see also Table 1). Both bromide and iodide were found to inhibit the reaction, and no products were isolated. For the oxyanions, nitrate, sulfate, and acetylacetonate, vinyla-tion products of these oxyanions in addition to the acetate vinylation products were found. Because of the increased complexity of these systems, they were not investigated further. All chloride-containing systems investigated—PdCl2, Na2PdCl4, (NH3)2PdCl2, and 7r-allylpalladium chloride—had similar reactivities and vinylation-product distributions. 

Bis(3-nitro-2,4-pentanediono)copper(II) was obtained by the nitration of copper(II) bisacetylacetone with N2O4 in benzene or chloroform solutions. The acetylacetonates of Ni(II), Pt(II), and Pd(II) also gave bis(3-nitro) compounds, although a palladium (II) compound could not be... 

The ligand acetylacetone was also successfully nitrated by the mixture of copper(II) nitrate trihydrate and acetic anhydride or by a mixture of chromium(III) nitrate trihydrate and acetic anhydride. In the former case, bis(3-nitro-2,4-pentanediono)copper(II) precipitated and was thereby protected from cleavage of the chelate rings. In the latter case, a mixture of products was formed, presumably the mono-, di-, and trinitrated chromium chelates (54). 

The introduction of substituents into the 3-position in acetylacetone is difficult and in some cases impossible unless the ligand is chelated. For example, the free ligand 3-nitroacetylacetone is unknown, but its chelates, bis(3-nitro-2,4-pentanediono)copper(II) or tris(3-nitro-2,4-pentanediono)-chromium(III), can be obtained by nitration of the metal chelate with a mixture of copper(II) nitrate and acetic anhydride (54). It is possible in this case that the pathway, as well as the rate of the ligand nitration, is altered as a result of chelate formation. 

The first report of a coordinated acetylacetone reaction was the bromination of the chromium(III) complex (equation 55). This was followed, more than 30 years later, by the nitration of copper(II) acetylacetonate with dinitrogen tetroxide (equation This result is... 

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Aluminum acetylacetonate 1,2-Butylene carbonate Chromic acetylacetonate Cobalt acetate (ous) Cobalt acetylacetonate Copper nitrate (ic) Ethylene carbonate Ferric acetylacetonate Hexyloxypropylamine Isodecyloxypropylamine N-lsodecyloxypropyl 1-1,3-diaminopropane Magnesium acetylacetonate Manganese acetylacetonate Methylamine Methylamine, aqueous solutions... 

The controlled precipitation of the salt mixture is very important in the case of semiconductor nanocrystals. Therefore, Ag-Pd and Cu-Pd colloids of different composition may be obtained by alcohol reduction of mixtures of silver nitrate or copper oxide with palladium oxide. Another study reports synthesis of Fe-Pt alloy nanocrystals by thermal decomposition of the Fe and Pt acetylacetonates in high-boiling organic solvents. The co-reduction of silver nitrate and chloroauric acid with sodium borohydride led to Au-Ag alloy nanocrystals. The utilization of lasers on Au-Ag layered particles determines the Au-Ag alloying and segregation (Jia et al. 2005). 

Recent examples of kinetic studies of substitution in organic ligands include a qualitative investigation of the halogenation of the copper(n) complex of 8-hydroxyquinoline by the halogens themselves or by iV-halogenosuccinimides, and the establishment of the relative reactivity of the 3-position of acetylacetone co-ordinated to chromium(m) and to cobalt(m) from the relative rates of nitration and of formylation of the complexes Cr(acac)s and Co(acac)3. ... 

Potassium 2-nitrobenzoate (22.6 g, 110 mmol), (l,10-phenanthroline)bis(triphenyl-phosphine)copper(I) nitrate (1.25 g, 1.50 mmol), and palladium acetylacetonate were diluted in deoxygenated, anhydrous mesitylene (150 mL), and 2-bromotoluene (12.3 mL, 100 mmol) was added under an atmosphere of nitrogen. The reaction mixture was stirred for 16 h at 150 °C internal temperature. After cooling to ambient temperature, the reaction mixture was filtered through a pad of Celite and the filter cake was rinsed with ethyl... 

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