Anions acetylacetonate

Figure 1-11. The resonance forms of some ligands that cannot be represented by a single valence bond structure (acetate anion, acetylacetonate anion and pyridine).

Nonanedione, another 1,3-difunctional target molecule, may be obtained from the reaction of hexanoyl chloride with acetonide anion (disconnection 1). The 2,4-dioxo substitution pattern, however, is already present in inexpensive, symmetrical acetylacetone (2,4-pentanedione). Disconnection 2 would therefore offer a tempting alternative. A problem arises because of the acidity of protons at C-3 of acetylacetone. This, however, would probably not be a serious obstacle if one produces the dianion with strong base, since the strongly basic terminal carbanion would be a much more reactive nucleophile than the central one (K.G. Hampton, 1973 see p. 9f.). 

Beryllium complexes, 3, 3 acetylacetone solvolysis, 2, 378 amides, 2, 164 amines, 3, 7 anionic, 3, 10 1,3-diketones... 

Chromium, (ri6-benzene)tricarbonyl-stereochemistry nomenclature, 1,131 Chromium complexes, 3,699-948 acetylacetone complex formation, 2,386 exchange reactions, 2,380 amidines, 2,276 bridging ligands, 2,198 chelating ligands, 2,203 anionic oxo halides, 3,944 applications, 6,1014 azo dyes, 6,41 biological effects, 3,947 carbamic acid, 2,450 paddlewheel structure, 2, 451 carboxylic acids, 2,438 trinuclear, 2, 441 carcinogenicity, 3, 947 corroles, 2, 874 crystal structures, 3, 702 cyanides, 3, 703 1,4-diaza-1,3-butadiene, 2,209 1,3-diketones... 

The compound 2,4-pentanedione (also known as acetylacetone and abbreviated to acac) is acidic and can be deprotonated. The anion forms complexes with metals that are used in gasoline additives, lubricants, insecticides, and fungicides, (a) Estimate the bond angles marked with arcs and lowercase letters in 2,4-pentanedione and in the acac ion. 

CHjCOCHgCOCHj + Na 6CiiH5 Na- (Cn3( 0CHC0CHj)" + HOCjHj The acetylacetone anion is a resonance hybrid ... 

A proton is easily removed to produce the acetylacetonate anion (abbreviated acac). 

The synthesis of the Ni(n) complex of the 13-membered (anionic) macrocycle (78) is also achieved using an in situ procedure (Cummings Sievers, 1970) in which triethylenetetramine, acetic acid, acetylacetone, and nickel acetate are heated in water at the reflux. Addition of iodide ion and adjustment of the pH of the solution to approximately 10, leads to crystallization of the Ni(n) complex of the required cyclized product (78) as its iodide salt. The reaction type has been extended to include Cu(ii) as the template metal (Martin, Wei Cummings, 1972) and has also been... 

The catalyst precursor generally used for the reaction is rhodium dicarbonyl acetylacetonate. However, detailed infrared studies under the reaction conditions (ca. 1000 bar CO/H2 and 200°C) have shown both the [Rh(CO)4] and the [Rh12(CO)34 36]2 anions to be present in various concentrations at different stages of the reaction (62, 63). It is suggested that rhodium carbonyl clusters, characterized as having three intense infrared absorptions at 1868 10, 1838 10, and 1785 10 cm-1, are responsible for the catalysis (62), and it is believed that the reaction is dependent upon the existence of the following equilibria ... 

Examples of w-allylnickel-X compounds (X = anionic ligand) other than 77-allylnickel halides which have been used in combination with (alkyl)aluminum halides as olefin oligomerization catalysts are 7r-allyl-nickel acetylacetonate (11) (Section III), 7r-allylnickel aziridide (4, 56), and bis(7r-allyl)nickel (6) (59). In addition to ir-allylnickel halides, organo-nickel halides such as tritylnickel chloride (60, 61) and pentafluoro-phenylbis(triphenylphosphine)nickel bromide (62), or hydridonickel halides, e.g., trans-hydridobis(triisopropylphosphine)nickel chloride (12) (Section III), give active catalysts after activation with aluminum halides... 

In Table 5 the values for the free standard enthalpies for the reactions of neutral donors and anion donors with vanadyl acetylacetonate are listed. It can be seen that towards the reference molecule iodide ion is a somewhat weaker ligand than propanediol carbonate, whereas the bromide ion is between tri-methylphosphate and acetone, and the chloride ion between DMF and DMSO 22>. The fluoride ion and the NCS -ion are stronger donors than all neutral donors but are somewhat weaker than the azide and the cyanide ion. 

The barriers to acetyl group rotation in 84a to d are at least as high as in the acetylacetonate anion (Table 18), indicating a considerable delocalization of negative charge into Ac—Q—Ac. As mentioned later (Table 19), the twist angle in 84a is 73°. ... 

In the protonation of conjugated systems, the rates of protonation at the two possible sites are different. So for example, the mesomeric anion of acetylacetone, [24], is protonated by the hydronium ion at... 

The acidity of a C-H is further enhanced if it is adjacent to two carbonyl groups, as in the 1,3-diketone acetylacetone. The enolate anion is stabilized by delocalization, and both carbonyl oxygens can participate in the process. This is reflected in the VK, 9 for the protons between the two carbonyls. 

Now for some interesting features of the reaction, though they become fairly obvious with a little thought. First, the central methylene contains the more acidic protons (pATa 9) since it is flanked by two carbonyls, so the enolate anion formed involves this carbon (see Section 4.3.5). In other words, alkylation occurs on the central carbon of acetylacetone, not on the terminal carbons. Second, it is possible to use carbonyl compounds such as acetone as a solvent without these reacting under the reaction conditions. Acetone will have similar acidity (pATa 19) to the acetyl groups of acetylacetone, so likewise will not... 

---