In the last decades, a variety of coordination modes of 2, 4-pentanedione(acetyl- acetone) and the β-diketone have been established in Pt(II) and Pd(II) complexes in which the β-diketone with an active methylene group displays the versatile function as neutral molecule, monoanion, dianion, or trianion, by Kawaguchi (1987). Despite of these extensive studies of metal-β-diketone complexes, there is only a brief reports of metal-tetraketone complexes. 1,1,2,2-Tetra-acetylethane and the bis(β-diketones) cryst allographically determined by X-ray or neutron diffraction methods are mostly in the dienol form in which intramolecular hydrogen bonding exist. Recent studies revealed that the central quarternary carbon(s) of 1,1,2,2-tetraacetylethane is however readily activated forming metal-carbon bonding. This review briefly summarizes some of these new linkage modes of the most simple bis(β-diketones), 1,1,2,2-tetraacetylethane, in addition of cleavages from 2,3-dithio and 2,3-diseleno-1,1,4,4-tetraacetylbutane, recently found in metal complexes.