Synthesis and Structural Characterisation of Lithium, Zinc, and Aluminium Pyrazolate Complexes

The reaction of nBuLi with 3,5-dimethylpyrazole (Me2pzH) in Et2O or tmeda/hexane (tmeda=N,N,N′,N′-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me2pzHNO2) in THF results in the formation of three structurally diverse lithium pyrazolates: namely an Et2O-solvated tetrameric complex [Li4(Me2pz)4(OEt2)4], bridged entirely with μ-η2:η1-pyrazolate bonding, a hexanuclear complex [Li6(Me2pz)6(tmeda)2] with four different coordination modes (μ-η1:η1, μ-η2:η1, μ3-η1:η2:η1 and μ3-η2:η2:η1), and a new polymeric compound [Li2(Me2pzNO2)2(thf)2]n, with [Li2(Me2pzNO2)2(thf)2] groups linked by –NO2 coordination. A mononuclear zinc complex [Zn(tBu2pz)2(tBu2pzH)2].1/2THF (tBu2pzH=3,5-di-tert-butylpyrazole) was prepared by reaction of tBu2pzH with ZnEt2, unidentate tBu2pz groups being stabilised by N–H⋯N hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph2pzH) with trimethylaluminium (mole ratio 3:1) in THF led to the formation of dinuclear [AlMe2(μ-Ph2pz)]2.1/2THF.