Syntheses And Catalytic Properties Of Copper Pyrazolate Complexes

Copper pyrazolate complexes have received much attention because of their richstructural chemistry and their potential applications in luminescence, magnetism andcatalysis. In this thesis, we selected1H-pyrazole-3,5-dicarboxylic acid dimethyl ester(Hdcmpz) and2-(1H-pyrazol-3-yl)-pyrazine (Hpyzpz) to react with a variety of coppersalts and isolated seven copper pyrazolate complexes with different structures and highcatalytic activity. I will introduce the main content from two parts.1. Reaction of Cu(OAc)2·H2O with Hdcmpz in MeOH at different reactiontemperature afforded three copper pyrazolate complexes. One tetranuclearCu(II)/pyrazolate complex [{Cu2(μ-OAc)2}2(μ-dcmpz)2-(μ-OAc)2](1) in89%yield wasobtained by reaction of Cu(OAc)2·H2O with Hdcmpz at room temperature. The similarreaction in refluxing MeOH produced a hexanuclear metalmacrocyclicCu(--) py azolate complex [{Cu(μ-dcmpz)}2(μ-OMe)2]3(2) in85%yield. Treatment ofthe same components under solvothermal condition resulted in the formation of anothertetranuclear Cu(II)/pyrazolate/carboxylate complex [{Cu(MeOH)}4(μ-mcccpz)4](3,Hmcccpz=5(3)-(methoxycarbonyl)-1H-pyrazole-3(5)-carboxylic acid) in30%yield.These complexes were characterized by IR spectra, elemental analysis， thermalgravimetric analysis and single-crystal X-ray diffraction analysis. It is found thatcomplexes1–3displayed high catalytic activity towards the condensation of nitrileswith2-aminoalcohol under solvent-free condition to produce various2-oxazolines.2. Reaction of Hpyzpz with Cu(NO3)2, CuI and Cu(OAc)2·H2O afforded onebinuclear complex [{(MeOH)Cu(NO3)}(μ-κ2:κ1-pyzpz)]2(4), one1D polymer[Cu(μ-κ2:κ1-pyzpz)2]n(5), and two2D polymers[CuICuII(μ-κ2:κ1-pyzpz)(μ3-κ2:κ1:κ1-pyzpz)(μ-I)]n(6),[Cu2(μ-κ2:κ1-pyzpz)(μ3-κ2:κ1:κ1-pyzpz)(OAc)(μ-OAc)]n(7). These complexes were alsocharacterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction analysis. Complexes4-7displayed high catalytic activity towards the condensationreaction of nitriles with2-aminoalcohol, producing the corresponding2-oxazolines.