Diketones coordination chemistry

Synthesis, coordination chemistry and analytical uses of monothio-/3-diketones Sulphinato complexes... 

Otway DJ, Rees WS (2000) Group 2 element beta-diketonate complexes, synthetic and structural investigations. Coordination Chemistry Reviews 210, 279-328... 

As hard metal centers, lanthanide(III) ions have a general preference for hard donor atoms (33,34). Much of their early coordination chemistry involved anionic oxygen donors and it is well established that carboxylates and (3-diketonates are very good at coordinating lanthanide ions. 

The coordination of /3-diketonates and related species to alkali and alkaline earth cations has long been recognized. Combes first prepared Be(acac)2 in 1887,255 and the contribution of Sidgwick and Brewer concerning the nature of dihydrated alkali metal /3-diketonates plays a seminal role in the development of this area of coordination chemistry.19 A review concerning the structure and reactivity of alkali metal enolates has been written, 6 and sections on alkali and alkaline earth /3-diketonates can be found within more generalized accounts of /3-diketone complexes.257,258... 

Some articles review the coordination chemistry of /3-diketones1529,1530 and, specifically, isomerism1531 and Lewis acid behaviour of the complexes.1532 Amongst the carbon-bonded /3-diketone complexes, those of nickel(II) have not been reported.1533... 

The importance of the chelate effect combined with the construction of multidentate ligands is well known in lanthanide chemistry. This is expressed in the rich coordination chemistry of / -diketonates [88] or complexes with Schiff bases [89] and macrocyclic polyethers [90] where lanthanide cations achieve steric saturation by high coordination numbers. Entrapment of the cation in a macrocyclic cavity results in greater complex stability. However, simply functionalized ligands such as ethanolamines can also supply a suitable ligand sphere [91-93],... 

Although formally an a-diketone, tropolone gives rise to a monoanion (equation 16) with coordination chemistry similar to that of the /3-diketonate anions. The tropolonate ion forms a five-membered chelate ring, which has a smaller Bite Angle (see Bite Angle) than /3-diketonate anions. This feature, in combination with its rigid planar nature, makes the tropolonate ion suitable for the formation of complexes... 

The synthetic flexibility of P-diketones has led to an explosion in the developments of related lanthanide complexes and their coordination chemistry. The [)-diketonate lanthanide complexes have been demonstrated to have variable coordination numbers ranging from six to ten, and diverse structural motifs. This family of complexes, having desirable luminescent properties... 

Vigato, P.A., Peruzzo, V., and Tamburini, S. (2009) The evolution of fS-diketone or fS-diketophenol ligands and related complexes. Coordination Chemistry Reviews, 253, 1099—1201. 

Arorm, G, Gamez, P, and Reedijk, J. (2008) Poly beta-diketones prime Ugands to generate supramolecular metalloclusters. Coordination Chemistry Reviews, 252, 964-989. 

One of the most versatile classes of ligands in coordination chemistry is that of the /3-diketonates, of which the most common is the acetylacetonate, (acac), Figure 9.1. The coordination chemistry of this ligand first appears in the literature in work by Combes in 1887-1894. Alfred Werner also published on the chemistry of the acac ligand in 1901. The acac ligand is remarkable in that it forms complexes with virtually any metal, including beryllium, lead, aluminum, chromium, platinum, and gadolinium. 

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