Immobilization acetylacetonates

Valente, A., A. M. Gotelho do Rego, J. J. Reis, I. F. Silva, A. M. Ramos, and J Vital, Oxidation of pinane using transition metal acetylacetonate complexes immobilized on modified activated carbon , Appl. Catal. A General, vol. 207, Issues 1-2, 1 February 201, pp 221-8. 

The polyitnide bead bearing a triazole residue was used to immobilize a stable and active Mo(VI) epoxidation catalyst. The polyimide was refluxed with molybdenyl acetylacetonate in ethanol for 3days. Upon completion, a polyimide-Mo complex catalyst was filtered and extracted with ethanol in a Soxhiet apparatus for 3 days. The supported complex was dried thoroughly under vacuum. The molybdenum content was measured by inductively coupled plasma (ICP) to be l.OSmmolg for PI-DAT.Mo and l. lOmmolg for CPI-DAT.Mo. 

As a rule, the formation of macromolecular metallocomplexes include a special design of macroligand, their functional groups, and MX with its own and frame ligands, which are retained in the inner coordination sphere of metal after immobilization. In addition to the halides, carbonyls, nitrosyls, phosphines, acetylacetonates and CH3COO-, pyridine and Dipy can also be used as frame ligands [35]. 

Polymeric VO(II) acetylacetonates are effective in the selective oxidation of anthracene by hydrogen peroxide to anthraquinone (up to 85%) in ethylacetate solution at 293-345 K. In spite of the fact that polymer-immobilized catalysts possess a high catalase-like activity in the decomposition of H2O2 [138] it has been proposed [125] that such metallopolymers may be valuable in the industrial catalytic oxidation of anthracene. 

An abundant scheme for the preparation of surface metal-organic complexes is ligand exchange, where one of the ligands of a metal complex in solution is substituted with a surface-confined ligand, leading to immobilization of the metal ion in the functional SAM. Examples of this process include Co and Os terpyri-dine complexes [22] Ru tetraamine [23] and dinuclear Ru [24] complexes salen complexes with Fe, Co, and Mn [25] and Zr acetylacetonate [26]. 

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