Paper
RSC Advances
ꢁ
1
2
5 4 3
.3.2.4 [5-(3-Chlorophenyl)-3-(p-tolyl)-4,5-dihydro-1H-pyrazol- (C ), 41.53 (C ), 21.53 (–CH ); IR (KBr, 4000–400 cm ): 3064,
1
3
-yl]-phenyl methanone (5d). Prepared by above method from n(C–H)ar stretching; 2948, n(C–H)al stretching; 1633, n(C]O); 1561,
-(3-chlorophenyl)-1-(p-tolyl) prop-2-en-1-one (3d) (6 mmol, 1.54 n(C]N); 1336, n(C]C); 1071, n(C–Br); 1035, n(C–N); 825,
g) and benzohydrazide (6 mmol, 0.82 g) aer 5–6 h reux; yield: (m-substituted aromatic ring); 789, n(C–H)ar bending. LC-MS (m/
ꢃ
2%; white amorphous solid. mp: $ 200 C; mol. wt. 374.86 z%): 419.05 (100) [M ], 421.20 [M + 2].
+
8
ꢁ1
g mol ; anal. calc. for: C H ClN O, calc. (found) (%): C, 73.69
2.3.2.7 [5-(4-Methoxyphenyl)-3-(p-tolyl)-4,5-dihydro-1H-pyrazol-
73.56); H, 5.11 (5.02); N, 7.47 (7.35); H NMR (400 MHz, CDCl - 1-yl]-phenyl methanone (5g). Prepared by above method from 3-(4-
2
3
19
2
1
(
3
0
d ) d/ppm: 2.415 (3H, s, 4 -CH ), 3.190 (1H, dd, J ¼ 5.2 Hz, 18.0 methoxyphenyl)-1-(p-tolyl) prop-2-en-1-one (3g) (6 mmol, 1.51 g)
1
3
Hz, 4-H
a
), 3.803 (1H, dd, J ¼ 12.0 Hz, 17.6 Hz, 4-H
b
), 5.79 (1H, dd, and benzohydrazide (6 mmol, 0.82 gm) aer 5–6 h reux; yield:
ꢃ
J
2
¼
5.2 Hz, 12.0 Hz, 5-H), 7.547–7.230 (9H, m, 79%; white amorphous solid. mp: $ 200 C; mol. wt. 370.44 g
00
00 00 00 000 000 000 000 000
0
0
ꢁ1
,4 ,5 ,6 ,2 ,3 ,4 ,5 ,6 -H), 7.624 (2H, d, J ¼ 8.0 Hz, 2 -H & 6 - mol ; anal. calc. for: C24
H N O , calc. (found) (%): C, 77.81
22 2 2
0
0
13
1
H), 8.067 (2H, d, J ¼ 7.2 Hz, 3 -H & 5 -H); C NMR (100 MHz, (77.75); H, 5.99 (5.80); N, 7.56 (7.45); H NMR (400 MHz, CDCl
-
3
0
CDCl
C100), 140.96 (C4
30.18 (C3
), 129.48 (C2000 000), 128.36 (C1
-d
3 1
) d/ppm: 164.29 (C]O), 160.99 (C
5
00), 154.69 (C
3
), 143.92
d
1
) d/ppm: 2.414 (3H, s, 4 -CH
3
), 3.212 (1H, dd, J ¼ 4.8 Hz, 17.6 Hz,
00
b
), 3.799 (3H, s, 4 -
(
1
(
(
0
), 134.82 (C1000), 131.07 (C4000), 130.27 (C3000 000), 4-H
a
), 3.774 (1H, dd, J ¼ 12.0 Hz, 17.6 Hz, 4-H
,5
0
0
0
), 127.94 (C
0 0
), 127.68 OCH
2 ,6
), 5.792 (1H, dd, J ¼ 4.8 Hz, 11.6 Hz, 5-H), 7.524–6.878 (9H,
,5
,6
3
0
0
00 00 00 000 000 000 000 000
0
C300), 126.77 (C200), 125.92 (C600), 123.99 (C 00), 60.72 (C ), 41.51 m, 2 ,3 ,5 ,6 ,2 ,3 ,4 ,5 ,6 -H), 7.632 (2H, d, J ¼ 8.4 Hz, 2 -H &
4
5
ꢁ
1
0
0
0
13
C
4
), 21.53 (–CH
3
); IR (KBr, 4000–400 cm ): 3071, n(C–H)ar; 2931, 6 -H), 8.045 (2H, d, J ¼ 6.8 Hz, 3 -H & 5 -H); C NMR (100 MHz,
n(C–H)al stretching; 1646, n(C]O); 1492, n(C]N); 1336, n(C]C); CDCl
-d
) d/ppm: 166.25 (C]O), 159.06 (C
000), 134.19 (C 00), 130.82 (C 000), 130.16 (C
), 127.59 (C
000,5000), 128.69 (C 000,6000), 127.09 (C
00,500), 60.68 (C
), 55.30 (–OCH
00), 154.76 (C
), 140.72
0 0
), 129.43
3 ,5
3
1
4
3
1
7
073, n(C–Cl); 1035, n(C–N); 825, (m-substituted aromatic ring); (C
91, n(C–H)ar bending, LC-MS (m/z%): 375 (100) [M ], 377 [M + 2]. (C
4
0
), 134.53 (C
1
1
4
+
0
0
0
), 126.75 (C
), 41.58 (C ), 21.52 (–CH
-yl]-phenyl methanone (5e). Prepared by above method from IR (KBr, 4000–400 cm ): 3042, n(C–H)ar stretching 2955
00,600),
3
);
3
1
2
2
,6
2
2
.3.2.5 [5-(4-Bromophenyl)-3-(p-tolyl)-4,5-dihydro-1H-pyrazol- 114.30 (C
3
5
3
4
ꢁ
1
1
3
1
;
-(4-bromophenyl)-1-(p-tolyl) prop-2-en-1-one (3e) (6 mmol, n(C–H)al stretching; 1691 n(C]O); 1510 n(C]N); 1332 n(C]C); 1108
.81 g) and benzohydrazide (6 mmol, 0.82 g) aer 5–6 h reux; n(C–N); 1256 n(C–O–C)sy; 1024 n(C–O–C)asy; 1075, 825 (p-
yield: 76%; white amorphous solid. mp: $ 200 C; mol. wt. substituted aromatic ring); 709 n(C–H)ar bending, LC-MS (m/z%):
ꢃ
ꢁ
1
+
4
19.31 g mol ; anal. calc. for: C23
H
19BrN
2
O, calc. (found) (%): 371 (100) [M ].
C, 65.88 (65.78); H, 4.57 (4.48); N, 6.68 (6.55); H NMR (400 MHz,
1
2.3.3 General synthesis of the complexes. The homoleptic
0
CDCl
3
-d
1
) d/ppm: 2.413 (3H, s, 4 -CH
3
), 3.176 (1H, dd, J ¼ 4.8 Hz, Ru(III) metal complexes (6a–6g) of the general formula
1
(
2
6
7.6 Hz, 4-H
a
), 3.798 (1H, dd, J ¼ 11.6 Hz, 17.6 Hz, 4-H
b
), 5.782 [Ru(L) ](PF was synthesized by the reactions of RuCl $3H
3
6
)
3
3
2
O
1H, dd, J ¼ 4.8 Hz, 11.6 Hz, 5-H), 7.542–7.229 (9H, m, with the respective ligands (5a–5g) in a 1 : 3 molar ratio in
0
0
0
00 00 00 000 000 000 000 000
0
,3 ,5 ,6 ,2 ,3 ,4 ,5 ,6 -H), 7.619 (2H, d, J ¼ 8.0 Hz, 2 -H & methanol.
0
0
13
III
-H), 8.045 (2H, d, J ¼ 7.6 Hz, 3 -H & 5 -H); C NMR (100 MHz,
-d ) d/ppm: 160.16 (C]O), 154.66 (C ), 140.97 (C
), 139.07 the precursor RuCl
00), 137.96 (C 000), 132.07 (C 000), 131.05 (C 000,5000), 10 min. Then a solution of ligand 5a (0.538 g, 0.15 mmol in
29.49 (C ), 128.39 (C ), 127.67 (C
000,6000), 127.57 (C 00,600), 126.76 50 mL methanol), was added and the reaction was reuxed
), 121.58 (C ), 41.43 (C ), 21.54 (–CH
00), 60.70 (C
); IR (KBr, overnight yielding a red-brown solution. The reaction was
000–400 cm ): 3057, n(C–H)ar stretching; 2950, n(C–H)al stretching
ltered to remove the residual undissolved material. Then,
627, n(C]O); 1492, n(C]N); 1336, n(C]C); 1029, n(C–Br); a saturated solution of excess KPF was added drop wise to the
010, n(C–N); 1070, 818, (p-substituted aromatic ring); 778, n(C– reaction mixture to complete precipitation and the mixture was
2.3.3.1 [Ru (5a)
3
](PF
6
)
3
(6a). A methanolic suspension of
CDCl
3
1
3
1
0
3
$3H
2
O (0.130 g, 0.5 mmol) was reuxed for
(
1
(
4
1
1
C
1
1
4
00,500), 130.16 (C
3 3
0
0
0
3
,5
1
2
2
C
2
0
,6
0
4
5
4
3
ꢁ
1
;
6
+
ꢃ
H)ar bending, LC-MS (m/z%): 420.95 (100) [M ], 422.80 [M + 2].
kept at 4 C overnight. The brown precipitate was ltered off,
2
.3.2.6 [5-(3-Bromophenyl)-3-(p-tolyl)-4,5-dihydro-1H-pyrazol- washed with water as well as diethyl ether and dried in vacuo at
ꢃ
1
3
1
-yl]-phenyl methanone (5f). Prepared by above method from 35 C. The proposed reaction for the synthesis of complexes 6a–
ꢃ
-(3-bromophenyl)-1-(p-tolyl) prop-2-en-1-one (3f) (6 mmol, 6g is shown in Scheme 1. Yield: 75.8%; mp: $ 300 C; meff: 1.86
ꢁ
1
.81 g) and benzohydrazide (6 mmol, 0.82 g) aer 5–6 h reux; BM; mol. wt. 1611.19 g mol ; anal. calc. for C69
H
F
N
O
-
57
21
6
3
ꢃ
yield: 78%; white amorphous solid. mp: $ 200 C; mol. wt.
3
P Ru, calc. (found) (%): C, 51.44 (51.22); H, 3.57 (3.40); N, 5.22
19.31 g mol ; anal. calc. for: C H BrN O, calc. (found) (%): (5.15); Ru, 6.27 (6.20); IR (KBr, 4000–400 cm ): 3073,
C, 65.88 (65.80); H, 4.57 (4.49); N, 6.68 (6.54); H NMR (400 MHz, n(C–H)ar stretching; 2927, n(C–H)al stretching; 1604, n(C]O); 1503,
ꢁ
1
ꢁ1
4
23 19 2
1
0
CDCl -d ) d/ppm: 2.345 (3H, s, 4 -CH ), 3.219 (1H, dd, J ¼ 5.2 Hz, n(C]N); 1340, n(C]C); 1229, n(C–F); 1162, n(C–N); 1100, (p-
3
1
3
1
8.0 Hz, 4-H
a
), 3.899 (1H, dd, J ¼ 12.0 Hz, 18.4 Hz, 4-H
b
6
), 5.769 substituted aromatic ring); 702, n(C–H)ar bending; 843, n(PF );
ꢁ
1
2
ꢁ1
(
2
6
1H, dd, J ¼ 5.2 Hz, 12.0 Hz, 5-H), 7.554–7.264 (9H, m, 560, n(Ru–N); conductance: 175 U cm mol ; UV-vis: l (nm)
0
0
0
00 00 00 000 000 000 000 000
0
ꢁ1
ꢁ1
,4 ,5 ,6 ,2 ,3 ,4 ,5 ,6 -H), 7.620 (2H, d, J ¼ 8.0 Hz, 2 -H & (3, M cm ): 575 (540), 308 (15 723), 237 (22 330).
13
III
0
0
-H), 7.892 (2H, d, J ¼ 7.2 Hz, 3 -H & 5 -H); C NMR (100 MHz,
-d ) d/ppm: 166.33 (C]O), 160.34 (C
00), 154.64 (C
44.19 (C100), 140.96 (C4
), 130.19 (C2000 000), 129.71 (C
2.3.3.2 [Ru (5b)
3
](PF
6
)
3
(6b). It was synthesized using
ꢃ
CDCl
3
1
5
3
), ligand 5b (0.538 g, 0.15 mmol). Yield: 74.0%; mp: $ 300 C; meff
:
-
ꢁ
1
1
(
(
0
), 134.12 (C1000), 131.07 (C4000), 130.88 1.88 BM; mol. wt. 1611.19 g mol ; anal. calc. for C69
), 128.84
57 21
H F
C3000 000), 130.56 (C
0
0
0 0
2 ,6
N
O
3
P
Ru, calc. (found) (%): C, 51.44 (51.20); H, 3.57 (3.41); N,
,5
3 ,5
,6
6
3
ꢁ
1
C300), 128.37 (C1
0
), 127.69 (C200), 126.78 (C600), 124.46 (C400), 60.69 5.22 (5.17); Ru, 6.27 (6.21); IR (KBr, 4000–400 cm ): 3072,
n(C–H)ar stretching; 2927, n(C–H)al stretching; 1630, n(C]O); 1489,
This journal is © The Royal Society of Chemistry 2015
RSC Adv., 2015, 5, 85350–85362 | 85353