Model Dizinc Phosphodiesterases
FULL PAPER
transesterification of BNPP in methanol to give MNPP and DMP,
dustrie (F.M.), OTKA TS 040685 (E.F.), and COST (D21/0001) is grate-
fully acknowledged.
2
.4 mmol of the complex (3, 4, 5 or 6) was first dissolved in 0.2 mL of
[
D ]DMSO, 4.8 mmol of BNPP in 0.6 mL of MeOH was then added, and
P NMR spectra recorded periodically. P NMR (121 MHz, [D ]DMSO/
6
6
3
1
31
MeOH, 298 K) in the presence of 3: d = 2.15 (s, br; DMP), ꢀ4.01 (s, br;
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MNPP), ꢀ12.13 ppm (s; BNPP); in the presence of 4: d = 2.73 (s;
3
1
DMP), ꢀ3.94 (s; MNPP), ꢀ12.12 ppm (s; BNPP); P NMR (121 MHz,
1
3
[
D
6
]DMSO/MeOH, 243 K, { H}-coupled, all
ence of 3: d = 3.32 (sept; free DMP), 1.96 (sept; bound DMP), ꢀ4.14
q; free MNPP), ꢀ5.09 (q; bound MNPP), ꢀ12.49 ppm (s; BNPP); in the
presence of 4: d = 3.35 (sept; free DMP), 2.61 (sept; bound DMP),
4.11 (q; free MNPP), ꢀ4.48 (q; bound MNPP), ꢀ12.47 ppm (s; BNPP).
J
P, H ꢄ 11 Hz) in the pres-
(
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pH potentiometric titrations: The pH potentiometric titrations were con-
ducted at 25.0ꢁ0.18C at an ionic strength of 0.2m (KCl) using a Radio-
meter PHM 84 pH-meter equipped with a Metrohm 6.0234.100 combined
electrode and a Metrohm dosimat 715. The electrode and pH-meter were
calibrated using a potassium biphthalate buffer at pH 4.008; the concen-
trations of the 0.2073m HCl and 0.1986m KOH stock solutions were
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checked and a pK
following Granꢁs method.
To prepare the samples, the ligands L and L were pipetted from 2
W
of 13.765 and an Irving factor of 0.082 were obtained
[
44]
1
2
1
97–206.
ꢀ
3
1
0
m stock solutions, each containing 0.032m HCl; zinc(ii) was taken
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from a 0.0979m ZnCl stock solution containing 0.0163m HCl. Additional
2
HCl was added in the form of the 0.2073m HCl stock solution and KCl
was taken from a 2m stock solution. The initial concentrations of the
1
2
samples were 0.2m KCl, 0.956 mm ligand L , 1.050 mm ligand L , and
1
2
1
5.60 mm HCl for L , 15.99 mm HCl for L . The initial ZnCl
tion was varied between 0.979 mm, 1.469 mm, and 1.860 mm for both L
2
concentra-
1
2
and L .
Titrations of the free ligands were performed between pH 2 and 11.5 (or
until precipitation) and for ligands with added metal ion solutions be-
tween pH 2 and 11 using a 0.1850m KOH stock solution. The pH-metric
results were utilised to establish the stoichiometries of the species and to
calculate the stability constants. Calculations were performed with the
[
45]
computer programs SUPERQUAD and PSEQUAD
and speciation
[
46]
curves were created with the help of the MEDUSA program.
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X-ray crystallography: Crystal data and experimental conditions are
listed in Table 4. Data were collected on a STOE image plate IPDS II
system (graphite-monochromated MoKa radiation, l = 0.71073 ) em-
ploying w scans at ꢀ1408C. All structures were solved by direct methods
[
47]
2
[48]
(
SHELXS-97) and refined against F using SHELXL-97. The non-
hydrogen atoms were refined anisotropically, except for those in disor-
dered parts. Hydrogen atoms attached to carbon atoms were refined
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using a riding model with Uiso(H) tied to Ueq(C) (3-(ClO
4
)
2
and 5-
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10023.
2
(
ClO
4
)
2
) or with a fixed isotropic displacement parameter of 0.08 (4-
and 6-(ClO ). The positional and isotropic thermal parameters
and 4-(ClO
were refined without constraints. Two methanol solvent molecules in 4-
ClO are disordered about two positions (occupancy factors: 0.922(7)/
.078(7) and 0.560(11)/0.440(11)), as are parts of the ligand (C4–N5:
.520(18)/0.480(18); C24–N8: 0.51(4)/0.49(4)), one methyl group in O P-
(0.62(3)/0.38(3)), the acetone solvent molecule (0.51(2)/0.49(2)),
(
ClO
4
)
2
4
)
2
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of the hydrogen atoms attached to O1/O2 in 3-(ClO
4
)
2
4 2
)
(
4 2
)
0
0
2
[
[
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(
OMe)
and one ClO
and FLAT restraints were applied to model the disorder, where appropri-
ate. CCDC-248511 (3-(ClO ), CCDC-248512 (4-(ClO ), CCDC-248513
5-(ClO ), and CCDC-248514 (6-(ClO ) contain the supplementary
2
ꢀ
4
4 2
anion (0.528(16)/0.472(16)) in 6-(ClO ) . SADI, DFIX,
4
)
2
4 2
)
(
4
)
2
4 2
)
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[
[
20]a) A. M. Barrios, S. J. Lippard, J. Am. Chem. Soc. 1999, 121, 11751–
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9
288–9294.
[
[
22]F. Meyer, P. Rutsch, Chem. Commun. 1998, 1037–1038.
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Acknowledgements
[24]D. Suꢂrez, E. N. Brothers, K. M. Merz Jr., Biochemistry 2002, 41,
615–6630.
6
Financial support from the Deutsche Forschungsgemeinschaft (F.M.,
project Me1313/5–1), the DAAD (B. B-S.), the Fonds der Chemischen In-
[25]S. Erhardt, E. Jaime, J. Weston, J. Am. Chem. Soc. 2005, 127, 3654–
3655.
Chem. Eur. J. 2005, 11, 4349 – 4360
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4359