p3 B-Diketonekkkkkkkkkkkkkkkkkkkkkkkkkkkkkkks.pptx

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1. B -Diketones and Related Ligands

2. 1.6.7 TRI-, TETRA-, AND POLYKETONES : Since 1950 several groups have synthesized -diketone ligands with additional functionalized fragments such as: triketones (1) heptane-2,4,6-trione

3. The first papers in this field reported the syntheses of (2)(where Y (CH2)4, (CH2)5, (CH2)6, (CH2)7, 1,3-C6H4, 1,4-C6H4, and 4,40 -C6H4C6H4) by condensation of bis(acyl chloride) with the sodium salt of a ketone and the remainder by Claisen condensation. + acyl chloride

4. Synthesis of (3) (where X (CH2)5CH3, 2-ClC6H4, 2-CH3OC6H4, 4-CH3OC6H4, 4-(CH3)2NC6H4, 3,4- (CH2O2)2C6H3, 2-C5H4N, 3-C5H4N, 4-C5H4N, C6H5, 4-HOC6H4),by condensation of the -diketone with the appropriate aldehyde in a 2:1 molar ratio. + diketone aldehyde

5. Other bis--diketones with different and more complex bridging fragments, like 1,4-piperazine, N-(o-tolyl) (4), 2,6-pyridyl (5), 4-CH3O2C-m-xylylene. . 1,4-piperazine, N-(o-tolyl)

6. A pentadentate bis--diketone (6) has been employed in its danionin form, yielding di nuclear complexes with Cu II and a trinuclear complex with Mn II.

7. Also Mg and Co derivatives, ligands (7) and (8), show the ability to include ammonium ions, affording ‘‘tetrahemispheraplexes’’ compound.

8. A trigonal tris-bidentate chelator with a central 1,3,5-phenylene fragment (9) produces tetranuclear tetrahedral and hexanuclear trigonal antiprismatic iron clusters. 1,3,5-phenylene

9. 1.6.7.1 Diketones with Substituents Containing Additional Donor Atoms: The 2-cyano-1,3-diketones (12) have been shown to form simple Co II and Cu II chelates stabilized by intermolecular contacts through the CN group.

10. The 3-acetylamido-pentane-2,4-dione ( amacH ) (13) is a highly enolized and acidic substance which is very soluble in water. The2-diazo-1,3-diketones (14) react with titanocene precursors affording 1-titana-2,n-diheterocyclic complexes. 2-(2-thiazolylazo)-1,3-diketones (15) and their corresponding metal derivatives have also been synthesized.

11. The3-(4-pyridyl)pentane-2,4-dione(3-pyacacH) (16) interacts with Cu2þ affording [Cu(3- pyacac )2] 2,5H2O 0,5thf, where the pyridyl fragment. A donor with a pyrazolyl moiety as the R2 substituent (3-pzacac) (17) produced a [Be(3-pzacac)2] complex with a supramolecular extended helical array.

12. A new -diketone (acacS2H) with a thiolate group in R2 (20) has been reported able to coordinate through either O2- and S2-chelating moieties, and to form mono-, di-, tri-, and tetranuclear complexes with several metal ions (Pt, Pd, Ag, Au, Cu, Ni, Cd, and Hg.

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