Metal acetylacetonates
Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M3 and M2. Mixed-ligand complexes, e.g. VO2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl. Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum and iridium.
Synthesis
A general method of synthesis is to treat a metal salt with acetylacetone, acacH:Addition of base assists the removal of a proton from acetylacetone and shifts the equilibrium in favour of the complex. Both oxygen centres bind to the metal to form a six-membered chelate ring. In some cases the chelate effect is so strong that no added base is needed to form the complex. Some complexes are prepared by metathesis using Tl.
Classification by triad
Titanium triad
Treatment of TiCl4 with acetylacetone gives cis-TiCl22, a red-coloured, octahedral complex with C2 symmetry:This reaction requires no base. The complex TiCl22 is fluxional in solution, the NMR spectrum exhibiting a single methyl resonance at room temperature.
Unlike Ti, Zr and Hf bind four bidentate acetylacetonates, reflecting the larger radius of these metals. Hafnium acetylacetonate and zirconium acetylacetonate adopt square antiprismatic structures.
Vanadium triad
is a blue complex with the formula V2. This complex features the vanadyl group, and many related compounds are known. The molecule is square pyramidal, with idealized C2v symmetry. The complex catalyzes epoxidation of allylic alcohols by peroxides. Vanadium acetylacetonate is a dark-brown solid. Vanadium β-diketonate complexes are used as precatalysts in the commercial production of ethylene-propylene-diene elastomers. They are often evaluated for other applications related to redox flow batteries, diabetes and enhancing the activity of insulin, and as precursors to inorganic materials by CVD.Chromium triad
, Cr3, is a typical octahedral complex containing three acac− ligands. Like most such compounds, it is highly soluble in nonpolar organic solvents. This particular complex, which has a three unpaired electrons, is used as a spin relaxation agent to improve the sensitivity in quantitative carbon-13 NMR spectroscopy. Chromium acetylacetonate is a highly oxygen-sensitive, light brown compound. The complex adopts a square planar structure, weakly associated into stacks in the solid state. It is isomorphous with Pd2 and Cu2.Manganese triad
It has been prepared by the comproportionation of the manganese compound Mn2 with potassium permanganate in the presence of additional acetylacetone. Alternatively the direct reaction of acetylacetone with potassium permanganate. In terms of electronic structure, Mn3 is high spin. Its distorted octahedral structure reflects geometric distortions due to the Jahn–Teller effect. The two most common structures for this complex include one with tetragonal elongation and one with tetragonal compression. For the elongation, two Mn–O bonds are 2.12 Å while the other four are 1.93 Å. For the compression, two Mn–O bonds are 1.95 Å and the other four are 2.00 Å. The effects of the tetragonal elongation are noticeably more significant than the effects of the tetragonal compression.Mn3, a one-electron oxidant, is used for coupling phenols.
Iron triad
, Fe3, is a red high-spin complex that is highly soluble in organic solvents. It is a configurationally labile, high-spin complex with five unpaired electrons. It is occasionally used as a catalyst precursor. Although configurationally labile, Fe3 has been partially resolved into its Δ and Λ isomers. The ferrous complex Fe2 is oligomeric.Like iron, Ru forms a very stable tris. Reduction of this Ru derivative in the presence of other ligands affords mixed ligand complexes, e.g. Ru22.
Cobalt triad
Co3 is low-spin, diamagnetic complex. Like other compounds of the type M3, this complex is chiral. Many such complexes have been resolved, but the premier example is Co3.The complex Co2, like the related nickel complex, exists octahedral complexes with two additional ligands. The anhydrous form exists as the tetramer 4. Like the trimeric nickel complex, this tetramer shows ferromagnetic interactions at low temperatures.
The synthesis of Co3 involves the use of an oxidant:
The two more popular acetylacetonates of rhodium are dicarbonylrhodium and Rh3. The former is a common precursor to homogeneous catalysts.
Ir3 and Rh3 are known. A second linkage isomer of the iridium complex is known, trans-Ir2. This C-bonded derivative is a precursor to homogeneous catalysts for C–H activation and related chemistries. Iridium derivatives include square-planar Ir2.
Nickel triad
exists as the trimetallic complex 3. It reacts with water to give the octahedral adduct , a chalky green monometallic complex. Bulky beta-diketonates give red, monomeric, square-planar complexes.In contrast to the complicated magnetism and structures of Ni2, platinum bis and palladium bis are diamagnetic monometallic species.
Copper triad
Cu2 is prepared by treating acetylacetone with aqueous. It is available commercially, catalyzes coupling and carbene transfer reactions.Unlike the copper derivative, copper acetylacetonate is an air-sensitive oligomeric species. It is employed to catalyze Michael additions.
Zinc triad
The monoaquo complex Zn2H2O is pentacoordinate, adopting a square pyramidal structure. The complex is of some use in organic synthesis. Dehydration of this species gives the hygroscopic anhydrous derivative. This more volatile derivative has been used as a precursor to films of ZnO.Acetylacetonates of the other elements
Colourless, diamagnetic Al3 is structurally similar to other tris complexes, e.g. . The trisacetylacetonates of the lanthanides often adopt coordination numbers above 8. In such cases, derivatives of acac− are more common.Variants of acac
Many variants of acetylacetonates are well developed. Hexafluoroacetylacetonates and trifluoroacetylacetonates form complexes that are often structurally related to regular acetylacetonates, but are more Lewis acidic and more volatile. The complex Eufod, Eu3, features an elaborate partially fluorinated ligand. This complex is a Lewis acid, forming adducts with a variety of hard bases.One or both oxygen centers in acetylacetonate can be replaced by RN groups, giving rise to Nacac and Nacnac ligands.