department, National University of Singapore. Water present
in the compounds was determined using a SDT 2980 TGA
Thermal Analyzer with a heating rate of 10 ЊC min in a N2
atmosphere using a sample size of 5–10 mg per run. Room
temperature magnetic susceptibility measurements were carried
out on a Johnson-Matthey Magnetic Susceptibility balance
added a filtered solution of H sgly (0.186 g, 1.00 mmol) in H O
2 2
(20 mL) with LiOH (0.024 g, 1 mmol). The resulting blue solu-
tion was stirred for about 2 h, filtered, and left for several days
to provide blue prism-like crystals, which were isolated by fil-
tration and air-dried. Yield: 0.423 g (77%). Anal. Calc. for
C H N O ClCu: C, 46.0; H, 3.9; N, 7.7; H O, 4.9. Found: C,
Ϫ1
2
1
22
3
8.5
2
Ϫ1
with Hg[Co(SCN) ] as standard for 1–9. Corrections for dia-
45.8; H, 3.8; N, 7.7; H O, 4.7%. IR (KBr, cm ): ν(OH) 3457,
2
Ϫ Ϫ
ν(NH) 2943, νas (COO ) 1604, ν (COO ) 1383, ν(C–O) (phen-
4
magnetism were made using Pascal’s constants. The reported
s
II
magnetic moments are per Cu ion. Variable temperature mag-
olic) 1260, ν(Cl–O) 1144 and 1090.
netic measurements were made for 5 using a Quantum Design
MPMS5 SQUID magnetometer in the 4.2–300 K temperature
range operating in an applied field of 1 T.
[Cu(Hsala)(phen)](ClO )ؒ0.625H O, 5. This complex was
4
2
obtained as blue prism-like crystals. Yield: 67%. Anal. Calc. for
C H N O ClCu: C, 48.2; H, 3.9; N, 7.7; H O, 2.1. Found:
Caution! Perchlorate salts are potentially explosive and should
be handled in small quantities, although we worked with these
2
2
21.25
3
7.625
2
Ϫ1
C, 48.4; H, 3.7; N, 7.4; H O, 1.9%. IR (KBr, cm ): ν(OH)
3363, ν(NH) 2947, ν as(COO ) 1600, ν (COO ) 1431, ν(C–O)
2
Ϫ
Ϫ
Ϫ
ClO4 salts without any incident. H sgly, H sala were syn-
2
2
s
thesized as reported in ref. [17]. The synthesis of the H sval
(phenolic) 1262, ν(Cl–O) 1146 and 1089.
2
ligand is described below.
[
Cu(Hsval)(phen)](ClO )ؒ1.5H O, 6. Blue crystals of 6 were
4 2
Ligand, N-(2-hydroxybenzyl) -L-ꢀ-valine (H sval)
2
obtained by following the procedure described for 4 but using
H sval instead of H sgly. Yield: 69%. Anal. Calc. for
2
2
To a solution of the -valine (1.17 g, 10 mmol) in 10 mL of H O
containing NaOH (0.40 g, 10 mmol) was added salicylaldehyde
2
C H N O ClCu: C, 48.6; H, 4.6; N, 7.0; H O, 4.6. Found: C,
2
4
27
3
8.5
2
Ϫ1
4
3
8.3; H, 4.4; N, 6.8; H O, 4.5%. IR (KBr, cm ): ν(OH)
2
Ϫ Ϫ
424, ν(NH) 2943, ν (COO ) 1624, ν (COO ) 1374, ν(C–O)
(
1.22 g, 10 mmol) in EtOH (10 mL). The yellow solution was
as
s
stirred for 30 min at room temperature prior to cooling in an ice
bath. The intermediate Schiff base solution was carefully
(
phenolic) 1256, ν(Cl–O) 1146 and 1090.
Alternatively, 4–6 have also been obtained quantitatively
adjusted to pH = 6.0–7.0 with HCl, then excess NaBH (0.46 g,
4
from the reaction between an aqueous solution of HClO and
4
1
2 mmol) was added in portions with gentle stirring while the
1
–3 respectively in MeOH.
yellow color slowly discharged. After 15 min the solution was
acidified to pH = 3.0–5.0 with concentrated HCl, left to stand
for 1 h. The resulting solid was filtered off, washed with MeOH
and Et O, dried and then recrystallized from H O–EtOH (1 : 1).
[
(phen)Cu(ꢁ-sgly)Cu(phen) ](ClO )2ؒ3H O, 7. To the green
2
4
2
solution formed from Cu(ClO ) ؒ6H O (0.371 g, 1.00 mmol)
4
2
2
2
2
in MeOH (15 mL) and phen (0.270 g, 1.50 mmol) in MeOH
10 mL) was added a filtered solution of H sgly (0.093 g,
Yield: 1.23 g (55%). mp 228–229 ЊC. Anal. Calc. for C H -
12
17
(
N O : C, 64.6; H, 7.6; N, 6.3. Found: C, 64.5; H, 7.7; N, 6.4%.
2
1
3
1
0.50 mmol) in H O (20 mL) with LiOH (0.024 mg, 1 mmol).
H NMR (DMSO-d ): δ 0.89 (d, 6H, J = 8.8Hz), 2.02 (m, 1H,
2
6
The resulting deep green solution was stirred for about 2 h,
filtered, and then left for several days to furnish green crystals,
which were isolated by filtration. Yield: 0.335 g (61%). Anal.
J = 7.2 Hz), 2.98 (d, 1H, J = 4.8 Hz), 3.79 and 3.92 (AB system,
H, JAB = 13.5 Hz), 6.74–6.79 (m, 2H), 7.11–7.20 (m, 2H).
2
Ϫ1
Ϫ
IR (KBr, cm ): ν(OH) 3446, ν(NH) 3175, ν (COO ) 1607, ν
as
s
Ϫ
Calc. for C H N O Cl Cu : C, 49.1; H, 3.6; N, 8.9; H O, 4.9.
45 39 7 14 2 2 2
Ϫ1
(
COO )1364, ν(C–O) (phenolic) 1265.
Found: C, 48.9; H, 3.5; N, 8.7; H O, 4.8%. IR (KBr, cm ):
2
Ϫ
Ϫ
ν(OH) 3420, ν(NH) 3064, ν (COO ) 1597, ν (COO ) 1427,
[
Cu(sgly)(phen)]ؒ2.75H O, 1
as
s
2
ν(C–O) (phenolic) 1277, ν(Cl–O) 1145 and 1090.
Cu (sala)(phen) ](ClO )2ؒ2.5H O, 8. Deep green crystals of
To the royal blue solution formed from Cu(OAc) ؒH O (0.200 g,
2
2
1
.00 mmol) in MeOH (15 mL) and phen (0.180 g, 1.00 mmol) in
[
2
3
4
2
MeOH (10 mL) was added a filtered solution of H sgly (0.186
2
8
were obtained by following the procedure described for 7
g, 1.00 mmol) in H O (20 mL) with LiOH (0.048 g, 2 mmol).
2
using H sala instead of H sgly. Yield: 68%. Anal. Calc. for
2
2
The resulting green solution was stirred for about 2 h and then
filtered, and left for several days. The yellow green crystals
formed were isolated by filtration and air-dried. Yield: 0.335 g
C H N O Cl Cu : C, 50.0; H, 3.6; N, 8.9; H O, 4.1. Found:
4
6
40
7
13.5
2
2
2
Ϫ1
C, 49.7; H, 3.6; N, 9.0; H O, 4.3%. IR (KBr, cm ): ν(OH)
423, ν(NH) 3033, ν as(COO ) 1596, ν (COO ) 1426, ν(C–O)
2
Ϫ
Ϫ
3
s
(
71%). Anal. Calc. for C H N O5.75Cu: C, 53.3; H, 4.7; N,
21 22.50 3
(
phenolic) 1267, ν(Cl–O) 1145 and 1090.
Cu (sval)(phen) ](ClO )2ؒ3H O, 9. This complex was
8
.9; H O, 10.5. Found: C, 53.6; H, 4.8; N, 9.1; H O, 10.2%. IR
2 2
Ϫ1 Ϫ
(
KBr, cm ): ν(OH) 3405, ν(NH) 2919, ν (COO ) 1609,
as
Ϫ
[
2
3
4
2
ν (COO ) 1387, ν(C–O) (phenolic) 1282.
s
obtained as deep green crystals by a procedure similar to that
described for 7 using H sval instead of H sgly. Yield: 71%.
2
2
[
Cu(sala)(phen)]ؒ3H O, 2. This complex was obtained as
2
Anal. Calc. for C H N O Cl Cu : C, 50.4; H, 3.9; N, 8.6;
48
45
7
14
2
2
yellow green crystals by a similar method described for 1. Yield:
7%. Anal. Calc. for C H N O Cu: C, 53.8; H, 5.1; N, 8.6;
H O, 3.7. Found: C, 50.1; H, 3.8; N, 8.8; H O, 4.0%. IR (KBr,
2
2
5
Ϫ1
Ϫ
Ϫ
22
25
5
6
cm ): ν(OH) 3421, ν(NH) 3045, ν (COO ) 1601, ν (COO )
as
s
H O, 11.0. Found: C, 53.5; H, 5.2; N, 8.4; H O, 11.1%. IR (KBr,
2
2
Ϫ
1
430, ν(C–O) (phenolic) 1273, ν(Cl–O) 1145 and 1090.
Ϫ1
Ϫ
cm ): ν(OH) 3425, ν(NH) 2931, ν (COO ) 1631, ν (COO )
as
s
When the synthesis was repeated with Cu(ClO ) ؒ6H O
4
2
2
1
384, ν(C–O) (phenolic) 1290.
(
instead of Cu(OAc) as described for 1–3), H L, phen, and
2
2
LiOH in the ratio of 1 : 1 : 1 : 2 in H O–MeOH, 7–9 were the
2
[
Cu(sval)(phen)]ؒ2H O, 3. This complex was prepared as
2
only products isolated in low yields. Further, 1–3 when reacted
with NaClO in the ratio of 1 : 1 in H O–MeOH, 7–9 were again
yellow green crystals using a procedure identical to that of 1
except that H sval was used in the place of H sgly. Yield: 75%.
Anal. Calc. for C H N O Cu: C, 57.7; H, 5.5; N, 8.3; H O, 7.2.
Found: C, 57.5; H, 5.4; N, 8.4; H O, 6.9%. IR (KBr, cm ):
4
2
2
2
the only products isolated.
24
27
3
5
2
Ϫ1
2
X-Ray crystallography
Ϫ
Ϫ
ν(OH) 3420, ν(NH) 2960, ν (COO ) 1630, ν (COO ) 1384,
as
s
ν(C–O) (phenolic) 1321.
The diffraction experiments were carried out on a Bruker AXS
23
SMART CCD diffractometer. The program SMART was
used for collecting the intensity data, for reflections indexing
[
Cu(Hsgly)(phen)](ClO )ؒ1.5H O, 4. To the green solution
4
2
23
formed from Cu(ClO ) ؒ6H O (0.371 g, 1.00 mmol) in MeOH
and for the determination of lattice parameters, SAINT was
4
2
2
(
15 mL) and phen (0.180 g, 1.00 mmol) in MeOH (10 mL) was
used for integration of the intensity of reflections and scaling,
D a l t o n T r a n s . , 2 0 0 3 , 8 8 0 – 8 8 9
881