Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

Journal Publication ResearchOnline@JCU
Rad, Nazli E.;Junk, Peter C.;Deacon, Glen B.;Taidakov, Ilya V.;Wang, Jun
Abstract

The reaction of nBuLi with 3,5-dimethylpyrazole (Me(2)pzH) in Et2O or tmeda/hexane (tmeda=N,N,N ',N '-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me(2)pzHNO(2)) in THF results in the formation of three structurally diverse lithium pyrazolates: namely an Et2O-solvated tetrameric complex [Li-4(Me(2)pz)(4)(OEt2)(4)], bridged entirely with mu-eta(2):eta(1)-pyrazolate bonding, a hexanuclear complex [Li-6(Me(2)pz)(6)(tmeda)(2)] with four different coordination modes (mu-eta(1):eta(1), mu-eta(2):eta(1), mu(3)-eta(1):eta(2):eta(1) and mu(3)-eta(2):eta(2):eta(1)), and a new polymeric compound [Li-2(Me(2)pzNO(2))(2)(thf)(2)](n), with [Li-2(Me(2)pzNO(2))(2)(thf)(2)] groups linked by -NO2 coordination. A mononuclear zinc complex [Zn(tBu(2)pz)(2)(tBu(2)pzH)(2)].1/2THF (tBu(2)pzH=3,5-di-tert-butylpyrazole) was prepared by reaction of tBu(2)pzH with ZnEt2, unidentate tBu(2)pz groups being stabilised by N-HN hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph(2)pzH) with trimethylaluminium (mole ratio 3:1) in THF led to the formation of dinuclear [AlMe2(mu-Ph(2)pz)](2).1/2THF.

Journal

Australian Journal of Chemistry

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73

ISBN/ISSN

1445-0038

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Issue

6

Pages Count

9

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Publisher

CSIRO Publishing

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DOI

10.1071/CH19417