Vb. Arion et al., Oxovanadium(IV) and oxovanadium(IV)-barium(II) complexes with heterotopic macrocyclic ligands based on isothiosemicarbazide, INORG CHIM, 317(1-2), 2001, pp. 33-44
The macrocyclisation reaction of 3,3'-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2
-hydroxy-benzaldehyde) (1) with S-methylisothiosemicarbazide hydroiodide in
the presence of barium triflate, followed by addition of oxovanadium(IV) c
hloride, yields the dimeric complexes [(VOBaLI)-I-1(I-3)CH3OH](2) (3) and [
VOBaL1((CFSO3)-S-3)(2)(CH3OH)(0.5)(H2O)(0.5)](2) (4). Starting from 3,3'-(3
,6,9-trioxaundecane-1,11-diyldioxy)-bis(2-hydroxybenzaldehyde (2), and foll
owing the same procedure the polymeric complex ([(VOBaLCl)-Cl-2]I-3)}(n) (5
) has been obtained. Treatment of 3, 4 or 5 in chloroform with an aqueous s
olution of guanidinium sulphate leads to VOL1 (6) or VOL2. 2H(2)O (7). Comp
ound 4 has been synthesised in high yield by direct complexation of VOL1 wi
th barium triflate in methanol. The crystal structures of 3, 4 and 5 have b
een determined by X-ray crystallography. Electronic, mass and EPR spectra a
re reported. (C) 2001 Elsevier Science B.V. All rights reserved.