III International Conference

PP-II-111CATALYTIC ACTIVITY OF POLYMER-FERROCYANIDE COMPLEXES INPARTIAL OXIDATION OF CYCLOHEXANE WITH HYDROGEN PEROXIDESelenova B.S.D.V. Sokolsky Institute of Organic Catalysis and Electrochemisrty MS&HE RK,Almaty, Republic of KazakhstanE-mail: alima@nursat.kzFerrocyanide complexes with different outosphere metal ions as well as the samecomplexes modified with polyhexamethyleneguanidine (PHMG) have been used as catalystsfor hydrogen peroxide decomposition and oxidation of cyclohexane with H 2 O 2 . The polymermodified ferrocyanide complexes showed higher activity and selectivity in partial oxidationof cyclohexane than corresponding inorganic complexes. The most stable catalyst forcyclohexane oxidation was Сu 2 [Fe(CN) 6 ] stabilized with PHMG.Currently catalytic systems on the basis of metal complexes with polymer ligands are ofgreat interest. The advantage of such systems is combinations of advantages of bothhomogeneous and heterogeneous catalysts. Besides, polymer-metal complexes in some kindare similar to enzimes regarding to their activity and selectivity under mild conditions.Achievement of high selectivity in partial hydrocarbon activation is a very important problem,solution of which is related to development of new catalysts including modified withpolymers.Catalyst for selective oxidation should have moderate red-ox properties so, we developeda method for synthesis of ferrocyanide complexes with polymer ligands.Polyhexamethyleneguanidin (PHMG) was selected as the ligand. Presence of nitrogencontaining groups enable the polymer to form insoluble complexes. Formation of the complexbetween PHMG and ferrocyanide was confirmed with IR-spectroscopy method.First, comparative activity of the polymer-metal complexes and inorganic complexes wasstudied in hydrogen peroxide decomposition. It was found that in acetonitrile solutionintensive decomposition of hydrogen peroxide proceed over potassium ferrocyanide; howeverconversion of Н 2 О 2 was at 80 %. Copper and iron(III) ferrocyanides are less active (4 hours),but the conversion was up to 100 %. Polymer-ferrocyanide complexes have similar activityand similar conversion rate as compared to that for inorganic complexes. At the same time,polymer-ferrocyanide complexes in acetonitrile solution are more active in cyclohexanepartial oxidation (Table1).367