Copper/Molybdenum Complexes: Synthesis,structure, And Study On Catalytic Activity

Cyclohexanol and cyclohexanone are the main products of cyclohexane oxidation,which are important organic materials for the production of adipic acid and caprolactam,and have important application in pharmaceuticals,paints,dyes and lubricating additives.Therefore,the cyclohexane oxidation receives more attention,and become one of the hottest topics in the field of catalysis.Since the high inertness of saturated hydrocarbons under mild conditions impedes their broad synthetic use,searching efficient catalyst for such reactions becomes more and more important.Herein,we studied the catalytic activity of ammonium paramolybdate?APM?for the cyclohexane oxidation firstly.By adding lactic acid as additives,the TON?Turn Over Number?reached 161.Two kinds of complexes were synthesized.One is novel oxomolybdenum?V?complexes:[?TpMoO???2-O?₂?MoOTp?]?Tp=tris?pyrazolyl?borate??1?and[(Tp^4-IMoOCl)??-O?(MoOClTp^4-I)](Tp^4-I=Hydrotris?4-iodinpyrazolyl?borate)?2?;and the other is novel Cu?II?complexes:[Cu₂?H₂L?₂?3,5-pyridinedicarboxylic??H₂O?]·2NO₃·2H₂O?H₂L=2,6-di-?5-methyl-1H-pyrazol-3-yl?pyridine??3?and[Cu?2,2'-bipy??ad?_1.5]·H₃O·2H₂O?H₂ad=hexane diacid??4?.All of the complexes are synthesized firstly,and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction.In addition,the catalytic performances of complexes 1-4 were studied firstly for the cyclohexane oxidation.By changing the kinds of acid additives and adding amount,the kinds of solvent,and the amount of oxidation agent,the TON of complexes 1-4reached 345,348,143,and 271,respectively.