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KAVUKCU ET AL.
2.28 (s, 3 H, p‐cymene‐CH3), 2.27 (m, 1 H, NCH2CH2N),
1.83 (m, 3 H, CH2), 1.37 (m, 2 H, CH2), 1.24 (d, JH‐
4.5 | Synthesis and characterization of Ru
complexes
= 6.8 Hz, 3 H, p‐cymene‐CH3), 0.93 (m, 6 H, p‐
H
cymene‐CH3 and CH3). 13C NMR (100 MHz, 303 K,
DMSO‐d6): δ 141.3, 136.7, 132.4, 130.1, 129.9, 128.9,
102.1, 100.7, 88.0, 87.4, 77.9, 57.5, 52.0, 47.8, 30.1, 29.3,
23.9, 21.2, 21.0, 20.5, 20.2, 19.3, 17.4, 13.7. 19F NMR
(376 MHz, 303 K, DMSO‐d6): δ 71.6 (d, JF‐F = 714.4 Hz,
PF 6). 31P NMR (161 MHz, 303 K, DMSO‐d6): δ −144.09
(septed, JP‐P = 710.0 Hz, PF6).
4.5.1 | Complex Ru1
C1 (1.00 g, 4.13 mmol) and [RuCl2(p‐cymene)]2 (1.26 g,
2.06 mmol) were dissolved in 20 ml dry MeCN. The mix-
ture was refluxed overnight. NH4PF6 (0.67 g, 4.13 mmol,
1 eq.) was dissolved with MeCN and added the mixture.
The mixture was filtered. The filtrate was evaporated to
dryness. The crude solid product was purified with col-
umn chromatography. Yield: 1.76 g (65%), red powder,
m.p.: 165–167 °C. Anal Calcd for C27H39ClF6N2PRu
(673,10): C, 48.18; H, 5.84; N, 4.16. Found: C, 48.34; H,
4.5.3 | Complex Ru3
The complex Ru3 was prepared in the same manner as
Ru1 using ligand C3 (1.00 g, 5.20 mmol), [RuCl2(p‐
cymene)]2 (1.59 g, 2.60 mmol) and NH4PF6 (0.84 g,
5.20 mmol). Yield: 2.30 g (73%), orange powder, m.p.:
162–164 °C. Anal Calcd for C23H37ClF6N2PRu (623.04):
C, 44.34; H, 5.99; N, 4.50. Found: C, 44.54; H, 6.11; N,
1
5.76; N, 4.02. H NMR (400 MHz, 303 K, DMSO‐d6): δ
8.76 (d, JH‐H = 7.6 Hz, 1 H, Ar‐H), 8.05 (t, JH‐
= 6.4 Hz, 1 H, Ar‐H), 7.91 (d, JH‐H = 8.0 Hz, 1 H,
H
Ar‐H), 7.65 (m, 4 H, Ar‐H), 6.82 (br, 1 H, NH), 6.64 (br,
1 H, NH), 5.38 (d, JH‐H = 6.0, 1 H, p‐cymene‐Ar‐H), 5.08
(d, JH‐H = 6.0 Hz, 1 H, p‐cymene‐Ar‐H), 4.47 (d, JH‐
1
4.58. H NMR (600 MHz, 303 K, DMSO‐d6): δ 7.51 (t,
= 6.0 Hz, 1 H, p‐cymene‐Ar‐H), 4.02 (d, JH‐
H
JH‐H = 6.4 Hz, 2 H, Ar‐H), 7.40 (d, JH‐H = 8.0 Hz, 2 H,
Ar‐H), 7.30 (t, JH‐H = 4.8 Hz, 1 H, Ar‐H), 6.71 (br, 1 H,
NH), 6.33 (br, 1 H, NH), 5.54 (d, JH‐H = 4.0, 1 H, p‐
cymene‐Ar‐H), 5.36 (d, JH‐H = 4.0 Hz, 1 H, p‐cymene‐
Ar‐H), 4.73 (d, JH‐H = 4.0 Hz, 1 H, p‐cymene‐Ar‐H),
4.59 (d, JH‐H = 4.0 Hz, 1 H, p‐cymene‐Ar‐H), 3.10 (m, 2
H, NCH2CH2N), 2.96 (m, 1 H, CH2), 2.84 (m, 2 H,
NCH2CH2N), 2.54 (m, 1 H, p‐cymene‐CH), 2.09 (s, 3 H,
p‐cymene‐CH3), 2.01 (m, 1 H, CH2), 1.66 (m, 2 H, CH2),
1.40 (m, 2 H, CH2), 1.16 (d, JH‐H = 4.4 Hz, 3 H, p‐
cymene‐CH3), 1.09 (d, JH‐H = 4.8 Hz, 3 H, p‐cymene‐
CH3), 0.95 (t, JH‐H = 4.8 Hz, 3 H, CH3). 13C NMR
(100 MHz, 303 K, DMSO‐d6): δ 150.3, 129.6, 126.3,
120.5, 106.6, 94.9, 86.0, 82.9, 81.4, 80.1, 56.2, 52.6, 48.6,
30.4, 30.3, 22.7, 21.5, 20.2, 17.2, 14.2. 19F NMR
(376 MHz, 303 K, DMSO‐d6): δ 69.2 (d, JF‐F = 713.2 Hz,
PF 6). 31P NMR (161 MHz, 303 K, DMSO‐d6): δ −144.03
(septed, JP‐P = 710.0 Hz, PF6).
= 6.0 Hz, 1 H, p‐cymene‐Ar‐H), 3.30 (m, 1 H, CH2),
H
3.16 (m, 2 H, NCH2CH2N), 2.91 (m, 2 H, NCH2CHN),
2.50 (m, 1 H, p‐cymene‐CH), 2.20 (m, 1 H, CH2), 1.94 (s,
3 H, p‐cymene‐CH3), 1.71 (m, 2 H, CH2), 1.38 (m, 2 H,
CH2), 1.09 (d, JH‐H = 6.8 Hz, 3 H, p‐cymene‐CH3), 1.01
(d, JH‐H = 6.8 Hz, 3 H, p‐cymene‐CH3), 0.95 (t, JH‐
= 7.2 Hz, 3 H, CH3). 13C NMR (100 MHz, 303 K,
H
DMSO‐d6): δ 146.3, 134.0, 128.9, 127.3, 126.3, 125.8,
125.7, 124.1, 115.3, 108.4, 93.1, 88.2, 84.2, 78.5, 77.4,
56.1, 52.8, 47.9, 30.5, 30.2, 22.6, 21.4, 20.3, 16.9, 14.2. 19F
NMR (376 MHz, 303 K, DMSO‐d6): δ 70.1 (d, JF‐
= 710.6 Hz, P F 6). 31P NMR (161 MHz, 303 K, DMSO‐
F
d6): δ −144.07 (septed, JP‐P = 710.0 Hz, PF6).
4.5.2 | Complex Ru2
The complex Ru2 was prepared in the same manner as
Ru1 using ligand C2 (1.00 g, 4.27 mmol), [RuCl2(p‐
cymene)]2 (1.30 g, 2.13 mmol) and NH4PF6 (0.67 g,
4.13 mmol). Yield: 2.05 g (74%), red powder, m.p.: 215–
217 °C. Anal Calcd for C26H43ClF6N2PRu (665,12): C,
46.95; H, 6.52; N, 4.21. Found: C, 46.82; H, 6.46; N, 4.32.
1H NMR (400 MHz, 303 K, DMSO‐d6): δ 6.99 (s, 1 H,
Ar‐H), 6.91 (s, 1 H, Ar‐H), 5.79 (d, JH‐H = 6.0 Hz, 1 H,
p‐cymene‐Ar‐H), 5.74 (br, 1 H, NH), 5.71 (br, 1 H, NH),
5.46 (d, JH‐H = 5.6 Hz, 1 H, p‐cymene‐Ar‐H), 4.99 (d, JH‐
4.5.4 | Ru4
The complex Ru4 was prepared in the same manner as
Ru1 using ligand C4 (1.00 g, 5.02 mol), [RuCl2(p‐
cymene)]2 (2.46 g, 2.51 mmol) and NH4PF6 (0.65 g,
5.02 mmol). Yield: 2.29 g (69%), yellow powder, m.p.:
130–132 °C. Anal Calcd for C27H45ClF6N2PRu (679.15):
C, 47.75; H, 6.68; N, 4.12. Found: C, 47.60; H, 6.75; N,
1
= 6.0 Hz, 1 H, p‐cymene‐Ar‐H), 4.71 (d, JH‐
4.24. H NMR (400 MHz, 303 K, CDCl3): δ 7.49 (t, JH‐
H
= 5.6 Hz, 1 H, p‐cymene‐Ar‐H), 3.54 (m, 1 H, CH2),
= 7.6 Hz, 2 H, Ar‐H), 7.33 (m, 3 H, Ar‐H), 5.75 (br, 1
H
H
3.27 (m, 2 H, NCH2CH2N), 2.92 (m, 1 H, NCH2CH2N),
2.60 (m, 1 H, p‐cymene‐CH), 2.56 (s, 3 H, mesityl‐CH3),
2.38 (s, 3 H, mesityl‐CH3), 2.29 (s, 3 H, mesityl‐CH3),
H, NH), 5.40 (br, 1 H, NH), 5.36 (m, 2 H, p‐cymene‐
Ar‐H), 4.76 (d, JH‐H = 5.6 Hz, 1 H, p‐cymene‐Ar‐H),
4.70 (d, JH‐H = 5.6 Hz, 1 H, p‐cymene‐Ar‐H), 3.49 (m, 1