Anhydrous tris acetylacetonate complexes

Structural analysis of several octahedral Sc(III) complexes have recently been reported. The structure 44) of anhydrous scandium-tris-acetylacetonate, Sc(acac)3, consists of discrete Sc(CH3COCHCOCH3)3 entity, with slight deviation from Dz symmetry. The coordination polyhedron around Sc (III) is a distorted... 

The j8-diketones are excellent chelating ligands for the rare earth ions and typical examples of the types of complexes that are formed are presented in table 25.14. (The functioning of these complexes as lasers is discussed in ch. 35.) The complexes that might have been expected, R(jS-diketone)3, rarely form, except for scandium, because of the tendencies of these compounds to add one or more additional ligands, particularly water molecules. Attempts to dehydrate most of these hydrated species leads either to destruction of the complex or the formation of polymeric hydroxo species (Pope et al., 1961). If, however, the substituents on the j8-diketone are large, t-butyl groups as an example, then the anhydrous tris chelate can be prepared (eisentraut and Sievers, 1965). The anhydrous trisacetylacetonato complexes have been prepared, however, in the absence of any possible adduct formation by the reaction of acetylacetone directly with a rare earth hydride (Przystal et al., 1971). The anhydrous acetyl-... 

The tris and bis complexes of acetylacetone (2,4-pentanedione) (167) with chromium(III) have been known for many years (168,169).739 The tris compound is generally prepared by the reaction of an aqueous suspension of anhydrous chromium(III) chloride with acetylacetone, in the presence of urea.740 Recently a novel, efficient synthesis of tris(acetylacetonato)chromium-(III) from Cr03 in acetylacetone has been reported.741 The crystal structure of the tris complex has been determined.744 A large anisotropic motion was observed for one of the chelate rings, attributed to thermal motion, rather than a slight disorder in the molecular packing. 

Tris[as-(diacetyltetracarbonylmanganese)] aluminum is preparedreadily by treating acetylpentacarbonylmanganese with 1 molar-equivalent of methyllithium at 0° followed by the addition of t/a molar-equivalent of anhydrous aluminum chloride. This complex is isostructural with tris(2,4-pentanedionato)aluminum (where 2,4-pentanedione = acetylacetone) except that the methine group is replaced formally by a Mn(C0)4 group, which suggests that the title compound is one example of a metallo-j3-diketonate type complex. 

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