S.M. Chopade et al. / Inorganica Chimica Acta 427 (2015) 72–80
75
77Se{1H} NMR (D2O) d: 218 (JPt–Se = 502 Hz); 195Pt{1H} NMR (D2O)
d: ꢁ3145 ppm.
2.2.8. [Pt(en)(dmpzCH2CH2SeCH2CH2COOH)][NO3][OH]ꢀH2O (8ꢀH2O)
Prepared in an analogous manner to 7 and isolated as a white
powder (43%), m.p. 210 °C (deco.). Anal. Calc. for C12H25N5O6Pt1Se1
ꢀH2O (FW 627.4): C, 22.97; H, 4.34; N, 11.16. Found: C, 22.53; H,
4.02; N, 11.52%. IR (
m
in cmꢁ1): 3430 (H2O), 3060 (OH), 1762
2.2.6. [Pt(NH3)2(dmpzCH2CH2SeCH2CH2COOH)][NO3]2 (6)
(CO), 1387, 825 (NO3). 1H NMR (D2O) d: 2.37, 2.38 (each s, 6H,
Me), 2.61 (br, s, 2H), 2.79 (br, 6H) (SeCH2CH2CO + SeCH2CH2N),
3.31 (s, 1H, unidentified), 5.59–5.98 (br, m, 4H, en N-CH2CH2),
6.17 (s, 1H, H4-dmpz); 13C{1H} NMR (400 MHz) (D2O) d: 10.7,
12.8 (dmpz-Me), 28.6 (1JSe–C = 55 Hz, SeCH2CH2CO), 29.6 (SeCH2
CH2N), 34.9 (SeCH2CH2CO), 46.8 and 48.0 (each t, en CH2), 49.1
(1JSe–C = 77 Hz, SeCH2CH2N), 107.8 (dmpz-4C), 144.6, 150.7
(dmpz-3C and 5C), 177.1 (C@O); 77Se{1H} NMR (D2O) d: 202
(JPt–Se = 392 Hz); 195Pt{1H} NMR (D2O) d: ꢁ3363 ppm.
Sticky white solid (45%). Anal. Calc. for C10H22N6O8Pt1Se1 (FW
628.4): C, 19.11; H, 3.52; N, 13.37. Found: C, 18.97; H, 3.05; N,
13.11%. IR (m
in cmꢁ1): 3125 (OH), 1720 (CO), 1385, 825 (NO3).
1H NMR (D2O) d: 2.39, 2.41 (each s, 6H, Me), 2.74–2.79 (br, m,
4H), 3.34–3.43 (br, m, 1H) (SeCH2CH2CO and SeCH2CH2N), 6.19 (s,
1H, H4-dmpz); 13C{1H} NMR (D2O) d: 10.6, 12.4 (each s, dmpz-
Me), 27.9 (SeCH2CH2CO), 29.3 (SeCH2CH2N), 32.6 (SeCH2CH2CO),
48.8 (JSe–C = 74 Hz, SeCH2CH2N), 107.9 (dmpz-4C), 144.4, 150.2
(dmpz-3C and 5C), 174.9 (C@O); 77Se{1H} NMR (D2O) d: 221
(JPt–Se = 501 Hz); 195Pt{1H} NMR (D2O) d: ꢁ3162 ppm.
2.2.7. [Pt(en)(dmpzCH2CH2SeCH2COOH)][NO3][OH]ꢀH2O (7ꢀH2O)
To a stirred methanolic solution (15 ml) of dmpzCH2CH2SeCH2
COOH (71 mg, 0.23 mmol), aqueous NaOH solution (0.13 M, 2 ml,
10 mg, 0.25 mmol) was added and stirred at room temperature
for 15 min. To this [Pt(en)(NO3)2] (103 mg, 0.27 mmol) was added
whereupon the reaction mixture turned clear within 10 min. The
stirring continued for 2 h. The solvent was evaporated in vacuo to
afford a white powder (85 mg, 54%) which was re-crystallized from
water (5%) acetone-ether mixture to give plate like colorless crys-
tals, m.p. 190 °C. Anal. Calc. for C11H23N5O6Pt1Se1ꢀH2O (FW 613.4):
2.2.9. [Pt(dmpzCH2CH2SeCH2CH2COOH)2][Cl]2 (9)
To a stirred CH2Cl2 solution (20 ml) of [PtCl2(PhCN)2] (128 mg,
0.27 mmol), dmpzCH2CH2SeCH2CH2COOH (76 mg, 0.29 mmol)
was added slowly with stirring at room temperature, initial clear
solution turned turbid. The reaction was further stirred for 2 h
and the precipitate was filtered through a G3 filtering unit and
washed with CH2Cl2 and the residue was dried in vacuo and
recrystallized from methanol to give pale yellow crystals of the
title complex (158 mg, 72%), m.p. 130 °C. Anal. Calc. for C20H32Cl2
N4O4Pt1Se2 (FW 816.5): C, 29.42; H, 3.95; N, 6.86. Found: C,
C, 21.54; H, 4.11; N, 11.41. Found: C, 21.42; H, 3.61; N, 11.30%. IR (
m
29.54; H, 3.89; N, 6.48%. IR (m
in cmꢁ1): 3455 (H2O), 3122 (OH),
in cmꢁ1): 3450 (H2O), 1635 (CO), 1366, 826 (NO3). 1H NMR (CD3
OD) (400 MHz) d: 2.46, 2.48 (each s, 6H, Me), 2.78–2.80 (br, 5H,
en N-CH2CH2 + SeCH2), 6.27 (s, 1H, H4-dmpz); 13C{1H} NMR (D2O)
d: 13.2, 15.2 (each s, dmpz-Me), 30.3 (s, SeCH2CO), 39.6 (s, SeCH2
CH2N), 49.0, 49.1 (SeCH2CH2), 49.2, 50.2, 50.3, 50.4, 51.44 (–CH2
CH2–), 110.3 (dmpz-4C), 147.0, 153.0 (dmpz-3C and 5C), 175.0
(C@O); 77Se{1H} NMR (D2O) d: 184 (JPt–Se = 397 Hz); 195Pt{1H}
NMR (D2O) d: ꢁ3358 ppm.
1746, 1715 (CO). 1H NMR (CD3OD) d: 1.94, 2.58 (each s, 6H, Me),
2.85–2.96 (br, m, 4H), 3.11–3.19 (br, m, 2H), 3.61, 3.65 (each br
s, 1H), 4.99–5.54 (br, m, 7H), 6.33 (s, 1H, H4-dmpz); 13C{1H}
NMR (CD3OD) d: 12.4, 13.7 (each s, dmpz-Me), 32.5 (SeCH2CH2CO),
33.0 (SeCH2CH2CO), 34.2 (NCH2CH2), 51.4 (1JSe–C = 68 Hz, NCH2
CH2), 110.3 (dmpz-4C), 147.1, 152.6 (dmpz-3C and 5C), 175.6
(C@O), 77Se{1H} NMR (CD3OD) d: 230 (1JPt–Se = 564 Hz); 195Pt{1H}
NMR (CD3OD) d: ꢁ3759 (1JPt–Se = 583 Hz) ppm.
Table 1
Crystallographic and structural refinement data for the compounds [Pt(en)(dmpzCH2CH2SeCH2COOH)][NO3][OH]ꢀH2O (7ꢀH2O) and [Pt(dmpzCH2CH2SeCH2CH2COOH)2][Cl]2ꢀ2H2O
(9ꢀ2H2O).
Compound
7ꢀH2O
11H25N5O7Pt1Se1
613.41
Colorless
9ꢀ2H2O
C20H36Cl2N4O6Pt1Se2
852.44
Chemical formula
Formula weight
Color
C
Colorless
Crystal size (mm)
Crystal system/space group
Unit cell dimensions
a (Å)
b (Å)
c (Å)
0.25 ꢂ 0.15 ꢂ 0.05
0.25 ꢂ 0.15 ꢂ 0.10
ꢀ
monoclinic/C2/c
triclinic/P1
7.5633 (17)
11.000 (2)
12.141 (5)
72.37 (2)
17.900(2)
9.891(2)
32.225(3)
90.000
a
(°)
b (°)
80.43 (3)
81.665 (18)
944.4 (5)
92.940(8)
90.000
5697.5(15)
8
c
(°)
V (Å3)
Z
2
Dcalc (g cm3)
2.157
1.988
l(Mo K
a
) (mmꢁ1)/F(000)
9.398/588
ꢁ9 6 h 6 9
ꢁ8 6 k 6 14
ꢁ15 6 k 6 15
2.74–27.52
4336
7.709/3296
ꢁ12 6 h 6 23
ꢁ12 6 k 6 7
ꢁ41 6 k 6 41
2.53–27.51
6543
Limiting indices
h range for data collection
No. of reflections collected
No. of independent reflections
Data/restraints/parameters
R indices [I > 2
R indices (all data)
3013
3357
4336/1/235
R1 = 0.0483, wR2 = 0.1122
R1 = 0.0993, wR2 = 0.1319
0.001
6543/0/313
R1 = 0.0810, wR2 = 0.2008
R1 = 0.1776, wR2 = 0.2402
0.001
r(I)]
(
(
D
D
/r)
max
q
)
max, (
D
q)
min
(Åꢁ3
)
1.690, ꢁ3.069
2.863, ꢁ3.163
Goodness-of-fit on F2
1.020
1.069