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Molybdenum Complexes: Structure, Properties and Applications (pp. 77-116) $100.00
Authors:  (Sevdalina Turmanova, Krassimir Vassilev, Department of Materials Science, Prof. Assen Zlatarov University, Burgas, Bulgaria, and others)
Abstract:
Molybdenum is ubiquitous and plays a complex role in the environment. It is a cofactor of enzymes which are essential in plants and animals, such as nitrogenase, nitrate reductase, sulfite oxidase and xanthine oxidase. The interactions of molybdenum with organic compounds have been the object of many studies. The preparation and characterization of molybdenum complexes based on different carriers with appropriate functional groups is one of the promising and interesting research fields in polymer chemistry that significantly broadens the prospective practical application of these materials. The reactions of co-ordination of polymer ligands with molybdenum ions and the formation of new structures of the resulting complexes have mainly been studied by employing spectral methods. The introduction of a metal into polymer macromolecules leads to changes in the polymer behavior and its surface morphology. The formation and structure of the polymer complex depend on factors such as the ligands, temperature, pH of the medium, etc.
Metal complexes were prepared on the basis of polymer ligands with carboxylic and nitrogen-containing functionalities by complexation with molybdenum ions in aqueous acidic solutions of Na2MoO4.2H2O or in organic solvents with different donor numbers with MoO2Cl2. The degree of introduction of molybdenum ions into the polymer matrices depended on the relative content of the functional groups in the polymers studied, such as polyacrylic acid, poly-4-vinylpyridine, poly(2-N,N-dimethylaminoethyl) methacrylate, poly(propylene imine) dendrimers, peptides and amino acids.
An attempt was made to evaluate the structure of the Mo-containing compounds by FTIR, UV-VIS spectroscopy, elemental analysis, EPR as well as NMR. The complexes have the necessary thermal stability to be used as catalysts in reactions taking place in the temperature interval 293-373○C. The influence of the molybdenum ion on the electrochemical characteristics of the materials was studied. The specific electric resistance and the tensile characteristics of the polymer metal complexes were found to depend on its content in the complex.
The polymer carriers with immobilized molybdenum ions were tested in a model reaction of oxidation of alkenes with organic hydroperoxide. The products of the oxidation reactions were identified by GC/MS analysis. The complexes of Mo (VI) and Mo (V) were studied several times in the test reaction to assess the change of their catalytic activity and it was proved that the latter remained unchanged.
New molybdenum improved complexes by surface modifications of polymers using different techniques (gamma and plasma treatment) were investigated. Based on these various polymers, new types of complexes with enhanced characteristics as immobilized catalysts for organic synthesis were also studied. 


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Molybdenum Complexes: Structure, Properties and Applications (pp. 77-116)