Four copper(II) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF2 or Cu(OH)(2)

作者：Mokuolu Q Folshade; Foguet Albiol Dolos; Jones Leigh F; Wolowska Joanna; Kowalczyk Radoslaw M; Kilner Colin A; Christou George; McGowan Patrick C; Halcrow Malcolm A^*

来源：Dalton Transactions, 2007, (14): 1392-1399.

DOI：10.1039/b618780c

Treatment of CuF2 with 2 equiv of 3{5}-[pyrid-2-yl] pyrazole (HpzPy), 3{5}- phenylpyrazole (HpzPh) or 3{5}-[4-fluorophenyl] pyrazole (HpzPhF) in MeOH, followed by evaporation to dryness and recrystallisation of the solid residues, allows solvated crystals of [{Cu(mu-pz(Py))(pz(Py))}(2)] (1), [{Cu(mu- pz(Ph))(2)}(4)] (2) and [Cu4F2(mu(4)-F)(mu-pz(PhF))(5)(Hpz(PhF))(4)] (3) to be isolated in moderate-to-good yields. Similar reactions of these three pyrazoles with Cu( OH) 2 in refluxing MeOH respectively afford 1, 2 and [Cu(pz(PhF))(2)(Hpz(PhF))(2)] (4) in ca. 10% yield. Crystalline 1 (.) 1/2H(2)O(.)2CHCl(3) contains two independent dinuclear molecules with a puckered di-(1,2-pyrazolido) bridge motif, linked by a bridging, hydrogen-bonding water molecule. Compound 2(.)1/2C(5)H(12), containing cyclic, square tetranuclear complex molecules, is the first homoleptic divalent metal pyrazolide to have a discrete molecular rather than polymeric structure, for a metal other than Pd or Pt. The two independent complex molecules in 3(.)3/4CH(2)Cl(2)(.)Hpz(PhF) contain a unique tetrahedral [Cu-4(mu(4)-F)](7+) core, three of whose edges are spanned by bridging pyrazolido groups. Magnetic data show that the copper centres in 1 and 3 are antiferromagnetically coupled, but that dried bulk samples of 2 do not retain their molecular structure.

• 出版日期2007