Unusual solid-state reaction of [{CrL(acac)}2(µ-H3O2)][PF6]3. Isolation and crystal structures of [CrL(acac)F]PF6and [CrL(acac)(O2PF2)]PF6(L = 1,4,7-trimethyl-1,4,7-triazacyclononane, acac = pentane-2,4-dionate)
- 1 January 1994
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 14,p. 2041-2048
- https://doi.org/10.1039/dt9940002041
Abstract
From a concentrated aqueous solution of the mononuclear complexes [CrL(acac)(OH)]PF6·H2O and [CrL(acac)(OH2)][ClO4]2 at pH ≈ 6 the dinuclear H3O2 –-bridged species [{CrL(acac)}2(µ-H3O2)][PF6]3 was isolated as a crystalline red solid (L = 1,4,7-trimethyl-1,4,7-triazacyclononane, acac = pentane-2,4-dionate). The dinuclear complex reacted at 145 °C in the solid state with evolution of 3 equivalents of HF, yielding quantitatively the mononuclear complexes [CrL(acac)F]PF6 and [CrL(acac)(O2PF2)]PF6 in equal amounts. Thus an unco-ordinated PF6 – anion is thermally converted into a co-ordinated fluoride and a monodentate O2PF2 – ligand. The crystal structures of [CrL(acac)(OH2)][ClO4]2, [CrL(acac)F]PF6 and [CrL(acac)(O2PF2)]PF6 have been determined by X-ray crystallography. The cobalt(III) complex [{CoL(acac)}2(µ-H3O2)][PF6]3 has also been prepared and structurally characterized. It is isostructural with the chromium analogue. Heating to its melting point at 190 °C did not induce solid-state transformation to mononuclear cobalt(III) species analogous to [CrL(acac)F]PF6 and [CrL(acac)(O2PF2)]PF6.Keywords
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