First (Peroxo)vanadium( V ) Complex with Heteroligand Formed in Reaction System − Synthesis, Structure and Reactivity of K[VO(O 2 )( omeida )]·H 2 O { omeida = N ‐[2‐(2‐oxomorpholine‐4‐yl)ethyl]iminodiacetato(2−)}
Abstract The crystalline peroxo complex of vanadium( V ), K[VO(O 2 )( omeida )]·H 2 O, where omeida is a δ‐lactone derivative, N ‐[2‐(2‐oxomorpholine‐4‐yl)ethyl]iminodiacetate(2−), has been obtained by reaction of vanadate with H 2 O 2 and N ‐(2‐hydroxyethyl)ethylenediaminetriacetic acid ( HEDTA ) i...
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| Published in | European journal of inorganic chemistry Vol. 2003; no. 11; pp. 2075 - 2081 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
| Published |
01.06.2003
|
| Online Access | Get full text |
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| Summary: | Abstract
The crystalline peroxo complex of vanadium(
V
), K[VO(O
2
)(
omeida
)]·H
2
O, where
omeida
is a δ‐lactone derivative,
N
‐[2‐(2‐oxomorpholine‐4‐yl)ethyl]iminodiacetate(2−), has been obtained by reaction of vanadate with H
2
O
2
and
N
‐(2‐hydroxyethyl)ethylenediaminetriacetic acid (
HEDTA
) in acidic aqueous solution at pH = 3 and 278 K. X‐ray analysis revealed a distorted pentagonal‐bipyramidal coordination around the vanadium atom, with a typical
cis
arrangement of oxo and peroxo ligands in apical and equatorial positions, respectively. Two amino nitrogen atoms of the tetradentate
omeida
(2−)‐N
1
,N
2
,O
1
,O
2
ligand occupy the neighbouring equatorial positions of the pentagonal plane, and two oxygen atoms of carboxymethyl groups bound to the same N1 nitrogen atom are in equatorial and apical positions. The six‐membered lactone ring in
omeida
was formed in the reaction solution from carboxy and hydroxy groups not involved in coordination with the vanadium atom. The
51
V NMR spectra of K[VO(O
2
)(
omeida
)]·H
2
O, and of peroxovanadate/
HEDTA
/H
2
O and vanadate/
HEDTA
/H
2
O solutions, as well as the
1
H NMR spectrum of
HEDTA
, proved that lactone ring closure proceeds only in peroxovanadate but not vanadate solutions. Spectroscopic investigation of the oxygen transfer reaction from the peroxo ligand in [VO(O
2
)(
omeida
)]
−
to the thiolato sulfur atom in [Co(
en
)
2
{S(CH
2
)
2
NH
2
}]
2+
or [Co(
en
)
2
(
cyst
)]
+
, and of the oxidation of
N
‐acetyl‐
L
‐cysteine by K[VO(O
2
)(
omeida
)]·H
2
O, revealed much more complicated reaction mechanisms than those of other (amino‐polycarboxylato)monoperoxo complexes of vanadium(
V
). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) |
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| ISSN: | 1434-1948 1099-0682 |
| DOI: | 10.1002/ejic.200200380 |