1
3
2
1
H). C NMR (126 MHz, DMSO-d
6
, 298 K): δ (ppm) 163.58, 155.90, 155.45, 155.04, 135.11,
34.34, 134.26, 132.69, 130.97, 130.26, 130.16, 119.67, 119.32, 117.77, 117.06, 114.88, 70.14, 62.43.
2.2. Synthesis of (PPh
4
)
2
[W(CN)
3
2
O(brsal)]·2H O (2)
5
-bromosalicylaldehyde (0.2013 g; 1 mmol) and 2-aminoethanol (0.060 ml; 1 mmol) were
dissolved in ethanol (15 ml) and refluxed for 15 minutes. Afterwards, the solution of
Na[W(CN) ]·6H O (0.5706 g; 1 mmol) in 37 ml water was added. The mixture changed colour
K
3
4
O
2
2
from yellow to dark green. The pH of the solution was lowered with 6M HCl to ca 8.5 and reflux was
continued for 20 minutes. Thereafter, the solution of tetraphenylphosphonium chloride (0.7500 g; 2
mmol) in 37 ml water was added. The resulting dark green crystals were filtered off and dried in air at
room temperature. Yield: 0.4746 g (38%). MW: 1235.78. Anal. Calcd. for C60
H
53BrN
4
O
5
P
2
W: C, 58.3;
, 298 K): δ
1
H, 4.32; N, 4.53%. Found: C, 58.4; H, 4.19; N, 4.48%. H NMR (500 MHz, DMSO-d
6
(ppm) 8.00 – 7.67 (m, 45H), 7.17 (d, J = 10.6 Hz, 1H), 7.13 (d, J = 2.7 Hz, 1H), 6.66 (dd, J = 8.8, 2.7
1
3
Hz, 1H), 6.32 (d, J = 8.8 Hz, 1H), 4.19 (s, 3H), 4.09 (t, J = 5.8 Hz, 2H). C NMR (126 MHz, DMSO-
d
6
, 298 K): δ (ppm) 164.36, 156.22, 155.84, 135.53, 134.76, 134.68, 130.68, 130.58, 120.97, 120.30,
1
18.19, 117.48, 70.55, 62.84.
2.3. Synthesis of (PPh
4
)
2
[W(CN)
3
2
O(metsal)]·5H O (3)
The synthetic procedure was analogous to the 1, however 5-metoxysalicylaldehyde (0.15 ml;
.2 mmol), 2-aminoethanol (0.075 ml; 1.25 mmol), K Na[W(CN) ]·6H O (0.6012 g; 0.95 mmol)
1
3
4
O
2
2
and tetraphenylphosphonium chloride (0.7412 g; 2 mmol) were used. Yield: 0.5422 g (41%). MW:
1
4
240.93. Anal. Calcd. for C61
H
62
N
4
O
9
P
2
W: C, 59.0; H, 5.04; N, 4.51%. Found: C, 58.6; H, 4.95; N,
1
.43%. H NMR (500 MHz, DMSO-d
6
, 298 K): δ (ppm) 8.00 – 7.63 (m, 59H), 7.15 (s, 1H), 7.00 (d, J
1
3
=
2.7 Hz, 1H), 6.73 (d, J = 2.7 Hz, 1H), 4.29 (t, J = 5.9 Hz, 1H), 4.24 – 4.04 (m, 4H). C NMR (126
MHz, DMSO-d , 298 K): δ (ppm) 159.35, 155.72, 155.52, 135.25, 134.50, 134.42, 131.64, 130.42,
30.32, 129.99, 121.62, 120.34, 117.93, 117.22, 114.13, 70.28, 62.58.
6
1
2.4. Synthesis of (PPh
4
)
2
[W(CN)
3
2
O(dclsal)]·H O (4)
The synthetic procedure was analogous to the 2, however 3,5-dichlorosalicylaldehyde (0.1913
g; 1 mmol), 2-aminoethanol (0.060 ml; 1 mmol), K Na[W(CN) ]·6H O (0.5684 g; 1 mmol) and the
solution of tetraphenylphosphonium chloride (0.7592 g; 2 mmol) in 42 ml water were used. Yield:
3
4
O
2
2
0
.2165 g (18%). MW: 1164.69. Anal. Calcd. for C58
H
45Cl
2
N
3
O
4
P
2
W: C, 59.8; H, 3.89; N, 3.61%.
1
Found: C, 60.0; H, 4.22; N, 3.82%. H NMR (500 MHz, DMSO-d
6
, 298 K): δ (ppm) 7.93 – 7.64 (m,
4
6H), 7.23 (s, 1H), 6.58 (s, 1H), 6.31 (s, 2H), 4.26 – 3.98 (m, 5H), 3.61 (d, J = 10.4 Hz, 3H), 3.53 (s,
4