Paper
Dalton Transactions
1
were dissolved in methanol (10 mL), and the mixture was heated Found: C, 40.63; H, 4.47; N, 8.26. H NMR (d
6
-DMSO,
to reflux and stirred for 4 h and filtered. Then ammonium hexa- 400 MHz) δ (ppm): 9.58 (s, 1 H), 8.52 (s, 1 H), 8.13 (dd, J =
1
2
fluorophosphate (0.39 mmol) was added to the solution and 6.8 Hz, J = 2.4 Hz, 1 H), 7.87 (s, 1 H), 7.83–7.80 (m, 1 H), 7.47
further stirred for 10 min. The solvent was removed under (t, J = 9.2 Hz, 1 H), 7.25 (s, 1 H), 6.57 (br s, 1 H), 5.83–5.80 (m,
vacuum and the residue was chromatographed by flash 1 H), 5.80–5.77 (m, 2 H), 5.72–5.70 (m, 1 H), 4.35 (br s, 1 H),
chromatography on silica gel using methanol/dichloromethane/ 4.25 (br s, 1 H), 3.98 (s, 1 H), 3.93 (s, 3 H), 3.71 (s, 1 H),
1
3
ammonia (1 : 20 : 0.2) as the eluent to give the target products.
Complex 7. Yellow powder (65.6 mg, 31.2%). Anal. Calc. for 100 MHz) δ (ppm): 156.6, 154.9, 153.1, 148.5, 137.2, 124.0,
PRu·2H O: C, 38.35; H, 4.17; N, 8.28%. 122.7, 119.4, 117.2, 109.2, 107.7, 103.0, 101.4, 99.6, 84.8, 82.5,
Found: C, 38.30; H, 4.26; N, 8.21. H NMR (d
6
2.84–2.55 (m, 6 H), 2.07–1.96 (m, 2 H). C NMR (d -DMSO,
C
27
H
31Cl
2
F
7
N
5
O
3
2
1
6
-DMSO, 81.8, 79.9, 79.5, 79.2, 67.6, 56.4, 56.4, 55.9, 55.5, 29.8, 29.6,
+
4
6
1
00 MHz) δ (ppm): 8.87 (s, 1 H), 8.10 (s, 1 H), 8.02 (dd, J = 28.1,
22.7.
FN
32ClFN
MS
Ru requires 674.1); 638.2 ([M
Ru requires 638.1).
(MALDI-TOF)
(m/z):
674.2
(M ,
1
+
.8 Hz, J
2
= 2.4 Hz, 1 H), 7.70–7.67 (m, 1 H), 7.58 (t, J = 2.8 Hz,
H), 7.32 (s, 1 H), 7.26–7.20 (m, 1 H), 6.68 (br s, 1 H), 5.83 (t,
C
C
29
H
H
33Cl
2
5
O
2
−
HCl] ,
29
5
O
2
J = 5.6 Hz, 1 H), 5.61 (t, J = 5.6 Hz, 1 H), 5.57 (d, J = 6.0 Hz),
Complex 11. Yellow powder (115.1 mg, 60.1%). Anal. Calc.
.45 (s, 2 H), 4.07 (s, 3 H), 3.88–3.86 (m, 1 H), 3.69 (t, J = 6.0 Hz, for C26 28ClF PRu·4H O: C, 38.55; H, 4.48; N, 10.37%.
H), 3.58–3.54 (m, 1 H), 2.69–2.65 (m, 2 H), 2.63–2.59 (m, 2 H), Found: C, 38.47; H, 4.54; N, 10.21. H NMR (d
4
2
2
1
1
8
H
6
N
6
O
2
2
1
6
-DMSO,
1
3
.34–2.31 (m, 1 H), 2.07–1.98 (m, 1 H). C NMR (d -DMSO, 400 MHz) δ (ppm): 8.84 (s, 1 H), 8.29 (s, 1 H), 8.10 (s, 1 H),
6
00 MHz) δ (ppm): 158.5, 156.8, 150.4, 149.3, 134.8, 126.9, 8.05 (d, J = 8.0 Hz, 1 H), 7.73 (d, J = 4.0 Hz, 1 H), 7.71 (s, 1 H),
25.6, 120.0, 119.8, 117.7, 117.5, 107.8, 104.6, 101.5, 84.7, 84.3, 7.42 (br s, 1 H), 5.79 (s, 6 H), 4.49 (m, 2 H), 4.06 (s, 3 H), 3.86
3.4, 81.5, 80.4, 79.8, 68.3, 60.5, 57.2, 53.7, 51.8, 45.9, 36.3. MS (s, 1 H), 3.63–3.53 (m, 2 H), 3.27 (s, 1 H), 2.71 (s, 2 H),
+
13
(
MALDI-TOF) (m/z): 664.2 (M , C27
6
H
31Cl
2
FN
Ru requires 628.1).
Complex 8. Yellow powder (100.2 mg, 47.9%). Anal. Calc. 126.9, 118.9, 112.1, 111.7, 108.1, 104.8, 104.6, 104.1, 100.0,
for C28 Pru H O: C, 40.84; H, 4.04; N, 8.50%. 83.9 (6 C), 68.4, 57.1, 53.5, 51.9, 46.0. MS (MALDI-TOF) (m/z):
Found: C, 40.78; H, 4.11; N, 8.47. H NMR (d
00 MHz) δ (ppm): 8.69 (s, 1 H), 8.08 (dd, J = 6.8 Hz, J = 4.8 C H N O Ru requires 557.1).
5 3
O
Ru requires 2.39–2.29 (m, 1 H), 2.10–1.97 (m, 1 H). C NMR (d
6
-DMSO,
+
5 3
64.1); 628.2 ([M − HCl] , C27H30ClFN O
100 MHz) δ (ppm): 158.3, 156.8, 149.2, 130.8, 129.7, 129.2,
H
31Cl
2
F
7
N
5
O
2
2
1
+
+
6
6 2
-DMSO, 593.1 (M , C26H28ClN O Ru requires 593.1); 557.2 ([M − HCl] ,
4
1
2
26 27 6 2
Hz, 1 H), 7.98 (s, 1 H), 7.77–7.73 (m, 1 H), 7.52 (t, J = 9.2 Hz,
Complex 12. Yellow powder (46.0 mg, 22.3%). Anal. Calc.
1
5
5
3
H), 7.31 (s, 1 H), 7.07 (br s, 1 H), 6.49 (br s, 1 H), 5.80 (d, J = for C30 36ClF PRu·H O: C, 44.37; H, 4.72; N, 10.35%.
H
6
N
6
O
2
2
1
.2 Hz, 1 H), 5.77 (d, J = 6.0 Hz, 1 H), 5.68 (t, J = 5.2 Hz, 1 H), Found: C, 44.48; H, 4.67; N, 10.28. H NMR (d -DMSO,
6
.64 (t, J = 5.2 Hz, 1 H), 4.42 (s, 2 H), 4.04 (s, 1 H), 3.96 (s, 1 H), 400 MHz) δ (ppm): 8.70 (s, 1 H), 8.33 (s, 1 H), 8.10–8.09 (m,
.86 (s, 1 H), 3.53–3.48 (m, 2 H), 3.30–3.20 (m, 2 H), 2.81–2.75 1 H), 7.99 (s, 1 H), 7.69–7.65 (m, 2 H), 7.33 (s, 1 H), 6.56 (br s,
(
m, 2 H), 2.33–2.27 (m, 1 H), 2.09–2.06 (m, 1 H), 2.00–1.97 (m, 1 H), 5.68 (d, J = 6.0 Hz, 1 H), 5.64 (d, J = 6.0 Hz, 1 H), 5.61 (d,
H). C NMR (d -DMSO, 100 MHz) δ (ppm): 157.4, 155.8, J = 6.0 Hz, 1 H), 5.56 (d, J = 6.0 Hz, 1 H), 4.47 (br s, 1 H), 4.39
6
1
3
1
1
1
5
52.0, 148.7, 136.1, 125.3, 124.1, 119.6, 117.3, 108.5, 104.0, (br s, 1 H), 4.04 (s, 3 H), 4.00–3.96 (m, 1 H), 3.88–3.83 (m, 1 H),
03.2, 101.0, 100.9, 83.3, 82.3, 81.3, 79.8, 79.2, 78.5, 68.1, 56.8, 3.69–3.57 (m, 1 H), 2.87–2.82 (m, 1 H), 2.73–2.71 (m, 1 H), 2.23
6.0, 53.7, 52.1, 45.5, 29.7, 22.7. MS (MALDI-TOF) (m/z): 660.2 (s, 3 H), 2.21 (s, 1 H), 2.15 (d, J = 4.0 Hz, 1 H), 2.09 (m, 1 H),
+
+
13
(
M , C28
H
31Cl
2
FN
5
O
2
Ru requires 660.1); 624.2 ([M − HCl] , 1.22 (d, J = 2.4 Hz, 3 H), 1.21 (d, J = 2.4 Hz, 3 H). C NMR (d
DMSO, 100 MHz) δ (ppm): 157.3, 155.7, 152.1, 148.7, 140.0,
Complex 9. Yellow powder (47.9 mg, 22.4%). Anal. Calc. for 130.6, 128.2, 127.8, 126.2, 119.1, 112.0, 108.8, 104.6, 103.8,
PRu·3H O: C, 38.32; H, 4.48; N, 7.98%. 96.7, 83.6, 82.3, 81.9, 81.5, 81.2, 80.7, 67.6, 56.8, 54.6, 51.4,
Found: C, 38.26; H, 4.53; N, 8.05. H NMR (d -DMSO, 45.8, 30.5, 22.8, 22.2, 17.4. MS (MALDI-TOF) (m/z): 649.2 (M ,
6
-
C H ClFN O Ru requires 624.1).
2
8
30
5 2
C
28
H
33Cl
2
F
7
N
5
O
3
2
1
+
6
+
4
6
1
5
00 MHz) δ (ppm): 8.84 (s, 1 H), 8.03 (s, 1 H), 8.01 (dd, J
.8 Hz, J = 2.4 Hz, 1 H), 7.71–7.68 (m, 1 H), 7.57 (t, J = 9.2 Hz,
H), 7.27 (d, J = 5.2 Hz, 1 H), 7.05 (br s, 1 H), 6.64 (br s, 1 H),
.87–5.82 (m, 2 H), 5.60–5.57 (m, 2 H), 5.55–5.53 (m, 1 H), 4.68 for C26
1
=
C
30
H
H
36ClN
6
O
2
Ru requires 649.2); 613.2 ([M
−
HCl] ,
2
C
30
N O Ru requires 613.2).
35 6 2
Complex 13. Yellow powder (52.2 mg, 24.7%). Anal. Calc.
31ClF PRu·2H O: C, 40.08; H, 4.53; N, 8.99%.
H
6
N
5
O
3
2
1
(
br s, 1 H), 4.41–4.25 (m, 3 H), 4.03 (s, 3 H), 3.98 (s, 2 H), Found: C, 39.87; H, 4.60; N, 9.18. H NMR (d
6
-DMSO,
3
2
.70–3.65 (m, 3 H), 3.38–3.24 (m, 2 H), 3.08–2.99 (m, 1 H), 400 MHz) δ (ppm): 8.81 (s, 1 H), 8.12 (s, 1 H), 7.44–7.39 (m,
1
3
.80–2.65 (m, 1 H), 2.60–2.54 (m, 2 H), 2.27–2.16 (m, 2 H).
-DMSO, 100 MHz) δ (ppm): 158.4, 156.8, 156.7, 150.3, H), 5.79 (s, 6 H), 4.54–4.37 (m, 2 H), 4.06 (s, 3 H), 3.98–3.88
49.7, 126.7, 125.4, 119.7, 117.7, 117.5, 107.8, 104.2, 101.4, (m, 2 H), 3.81 (s, 3 H), 3.60–3.48 (m, 3 H), 2.76–2.64 (m, 2 H),
C
2 H), 7.32–7.25 (m, 2 H), 6.91 (d, J = 8.4 Hz, 1 H), 6.86 (br s, 1
NMR (d
6
1
1
5
1
3
00.2, 85.8, 84.6, 84.0, 83.5, 81.7, 79.5, 67.7, 60.5, 57.1, 52.4, 2.40–2.27 (m, 1 H), 2.09–1.96 (m, 1 H). C NMR (d
6
-DMSO,
+
0.4, 45.7, 36.4, 28.1. MS (MALDI-TOF) (m/z): 678.2 (M , 100 MHz) δ (ppm): 160.0, 158.5, 156.7, 150.2, 149.2, 138.5,
+
C H Cl FN O Ru requires 678.1); 642.2 ([M
−
HCl] , 137.6, 130.2, 117.2, 112.1, 111.1, 107.8, 104.8, 101.6. 83.9 (6 C),
2
8
33
2
5
3
C
28
H
32Cl
2
FN
5
O
3
Ru requires 642.1).
68.4, 57.1, 55.8, 53.5, 51.8, 46.0. MS (MALDI-TOF) (m/z): 598.1
+
+
Complex 10. Yellow powder (71.6 mg, 33.2%). Anal. Calc. (M , C26
5 3
H31ClN O Ru requires 598.1); 562.2 ([M − HCl] ,
for C H Cl F N O PRu·2H O: C, 40.71; H, 4.36; N, 8.19%. C H N O Ru requires 562.1).
2
9
33
2
7
5
2
2
26 30 5 3
Dalton Trans.
This journal is © The Royal Society of Chemistry 2015