Bioinorganic Chemistry
FULL PAPER
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
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2
+
Catecholase activity studies: The catecholase activity of I was evaluat-
ed by reaction with 3,5-di-tert-butylcatechol at 258C in methanol. The ab-
ꢀ
1
ꢀ1
sorption at 400 nm (e=1400m cm ), characteristic of the formed qui-
none, was measured as a function of time. The experiments were run
under 1 atm of dioxygen. The kinetic parameters were determined for 2
ꢀ
5
1
0
m solutions of the complex (for simplicity, the complex concentration
throughout the article has been calculated based on the molecular weight
of dinuclear species ([Cu ([22]pr4pz)(CO (H O)]-
(CF ·CH CN·2H O) and 0.05–3 mm solutions of the substrate. In a
2
A
H
R
U
G
3
)
A
H
R
N
2
A
C
H
T
R
E
U
N
G
3
SO
3
)
2
3
2
2
+
typical catalytic experiment, 2.5 mL of the solution of I were placed in
a 1 cm path-length cell, and the solution was saturated with dioxygen. Af-
terwards, 75 mL of the solution of substrate were added. After thorough
shaking, the changes in UV/Vis spectra were recorded over a period of
3
0 min.
Effect of dihydrogen peroxide on the kinetics of DTBCH
effect of dihydrogen peroxide on the reaction rates was studied in dioxy-
gen-saturated methanol by varying the concentration of H in the
range of 0.01–1 mm at constant concentrations of the complex (210 m)
and DTBCH (1 mm).
Effect of 3,5-DTBQ on the kinetics of DTBCH
2
oxidation: The
2
O
2
ꢀ
5
2
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[
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2
oxidation: The effect of
DTBQ on the reaction rates was studied in dioxygen-saturated methanol
by varying the concentration of DTBQ in the range of 0.01–0.412 mm at
constant concentrations of the complex and DTBCH
2
. The concentration
of I was 210 m; the concentration of DTBCH was 0.2 mm and
mm.
Detection of dihydrogen peroxide in the catalytic DTBCH
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2
+
ꢀ5
2
1
[
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2
oxidation:
The presence of dihydrogen peroxide in the reaction mixture was ana-
ꢀ
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lyzed using the iodiometric assay based on I
3
, which has a characteristic
ꢀ
1
ꢀ1
absorption band at 353 nm (e=26000m cm in water). The oxidation
2
+
reaction of DTBCH
experiment. When the formation of quinone reached a desired value at
00 nm the solution was acidified with H SO to pH 2 to stop the reac-
tion. Water (3 mL) was added and the reaction mixture was then extract-
ed with CH Cl (2) to remove the formed DTBQ. A solution of KI
1 mL, 0.3m) in water with a catalytic amount of lactoperoxidase, to ac-
2
by I was carried out as described in the kinetic
4
2
4
2
2
(
ꢀ
3
, was added to a 2 mL aliquot of the aqueous
celerate the formation of I
layer. Blank experiments were performed under identical conditions in
2
+
ꢀ
the presence of DTBQ and I , but only minor formation of I
3
was ob-
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1
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Support of the NRSC Catalysis (a Research School Combination of
HRSMC and NIOK) is kindly acknowledged. Also support and sponsor-
ship concerted by COST Action D21/003/2001 is gratefully acknowl-
edged. Collaborative travel grant from the French Ministry of Research
and Foreign Affairs (EGIDE) and NWO (Van Gogh Programme and
CW: M.L. and A.L.S.), allowing visits and exchanges between Leiden and
Grenoble, is gratefully acknowledged. The work was in part supported by
CNRS/DFG program with a grant for K.S. The authors thank the Insti-
tute of Metals in Biology of Grenoble that provided the facilities for per-
forming 13 K EPR, and Dr. StØphane MØnage for assistance in these ex-
periments.
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Chem. Eur. J. 2006, 12, 6138 – 6150
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