posted on 2011-11-21, 00:00authored byOindrila Das, Sayantan Paria, Ennio Zangrando, Tapan Kanti Paine
The mononuclear copper(II) complex [Cu(H2L1)2(H2O)](ClO4)2 (1) (where H2L1 = 1,10-phenanthroline-5,6-dioxime)
reacts with copper(II) perchlorate in acetonitrile at ambient conditions
in the presence of triethylamine to afford a copper(II) complex, [Cu(L3)2(H2O)](ClO4)2 (2a), of 1,10-phenanthroline furoxan. A similar complex
[Cu(L3)2Cl](ClO4) (2) is isolated from the reaction of H2L1 with
copper(II) chloride, triethylamine, and sodium perchlorate in acetonitrile.
The two-electron oxidation of the vic-dioxime to
furoxan is confirmed from the X-ray single crystal structure of 2. An intermediate species, showing an absorption band at
608 nm, is observed at −20 °C during the conversion of 1 to 2a. A similar blue intermediate is formed
during the reaction of [Cu(HDMG)2] (H2DMG =
dimethylglyoxime) with ceric ammonium nitrate, but H2DMG
treated with ceric ammonium nitrate does not form any intermediate.
This suggests the involvement of a copper(II) complex in the intermediate
step. The intermediate species is also observed during the two-electron
oxidation of other vic-dioximes. On the basis of
the spectroscopic evidence and the nature of the final products, the
intermediate is proposed to be a mononuclear copper(II) complex ligated
by a vic-dioxime and a dinitrosoalkene. The dinitrosoalkene
is generated upon two-electron oxidation of the dioxime. The transient
blue color of the dioxime-copper(II)-dinitrosoalkene complex may be
attributed to the ligand-to-ligand charge transfer transition. The
intermediate species slowly decays to the corresponding two-electron
oxidized form of vic-dioxime, i.e. furoxan and [Cu(CH3CN)4](ClO4). The formation of two isomeric
furoxans derived from the reaction of an asymmetric vic-dioxime, hexane-2,3-dioxime, and copper(II) perchlorate supports
the involvement of a dinitrosoalkene species in the intermediate step.
In addition, the oxidation of 2,9-dimethyl-1,10-phenanthroline-5,6-dioxime
(H2L2) to the corresponding furoxan and subsequent
formation of a copper(I) complex [Cu(L4)2](ClO4) (3) (where L4 = 2,9-dimethyl-1,10-phenanthroline
furoxan) are discussed.