Inorganic Chemistry
Article
General Procedure for Complex Synthesis (1a−9a).
[RuCl2(p-cymene)]2 (0.10 mmol), 1H-pyrazole (0.19−0.21 mmol),
NEt3 (0.6 mmol), and the desired naphthoquinones (1−9) (0.19−
0.21 mmol) were dissolved in 8−12 mL of methanol and stirred at
50−60 °C for 12−15 min under microwave irradiation. The solvent
was removed, and the residue was purified by flash chromatography
(SiO2) with a ternary eluent system (EtOAc/n-hexane/NEt3 or
EtOAc/MeOH/NH4OH). The fractions were combined, evaporated,
and dried in vacuo. Oily residues were dissolved in dichloromethane,
precipitated with n-hexane, separately washed with n-hexane, and
dried in vacuo.29
(Carom.), 131.2 (Carom.), 127.9 (Carom.), 127.7 (Carom.), 127.1
(C5′), 112.3 (C3), 108.7 (C4′), 101.3 (Cd), 98.6 (Ca), 94.9 (C1),
83.3 (Cc), 82.9 (Cc), 80.2 (Cb), 80.1 (Cb), 32.7 (Ce), 23.1 (Cf),
22.8 (Cf), 18.3 (Cg), 16.9 (C9), 13.7 (C10). Elemental analysis
found: C, 58.83; H, 5.17; N, 5.47; O, 10.20. Calcd for
C25H26N2O3Ru(H2O)0.2: C, 59.21; H, 5.25; N, 5.52; O, 10.10%.
[3-Cyclohexyl-4-oxo-(1H-κN2-pyrazol-1-yl)-1,4-dihydronaphta-
lene-1,2-bis(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)] (4a). The
reaction was performed according to the general procedure using
[RuCl2(p-cymene)]2 (55 mg, 0.09 mmol), 1H-pyrazole (13 mg, 0.19
mmol), 4 (49 mg, 0.19 mmol), and NEt3 (75 μL, 55 mg, 0.54 mmol).
The mixture was stirred at 60 °C for 15 min under microwave
irradiation. Flash chromatography with EtOAc/n-hexane/NEt3 (70/
[4-Oxo-1-(1H-κN2-pyrazol-1-yl)-1,4-dihydronaphtalene-1,2-bis-
(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)] (1a). The reaction was
performed according to the general procedure using [RuCl2(p-
cymene)]2 (150 mg, 0.25 mmol), 1H-pyrazole (35 mg, 0.52 mmol), 1
(132 mg, 0.76 mmol), and NEt3 (342 μL, 248 mg, 2.45 mmol). The
mixture was stirred at 50 °C for 15 min under microwave irradiation.
Flash chromatography with EtOAc/MeOH/NH4OH (88/10/2).
1
25/5). Yield: 57 mg of yellow/greenish solid (0.10 mmol, 56%). H-
NMR (600.10 MHz, DMSO-d6) δ 8.40 (dd, J = 2.1, 0.7 Hz, 1H, H3′),
7.95−7.89 (m, 1H, Harom.), 7.53−7.47 (m, 2H, Harom.), 7.46−7.42
(m, 1H, Harom.), 6.66 (dd, J = 2.5, 0.7 Hz, 1H, H5′), 6.29 (dd, J =
2.3, 2.3 Hz, 1H, H4′), 6.03 (d, J = 5.9 Hz, 1H, Hc), 5.96 (d, J = 5.9
Hz, 1H, Hc), 5.67 (d, J = 5.9 Hz, 1H, Hb), 5.59 (d, J = 5.8 Hz, 1H,
Hb), 2.81−2.73 (m, 2H, He and H9), 2.25 (s, 3H, Hg), 2.07−1.96
(m, 1H, Hhexyl), 1.85−1.75 (m, 1H, Hhexyl), 1.69−1.57 (m, 3H,
Hhexyl), 1.27 (d, J = 2.4 Hz, 3H, Hf), 1.25 (d, J = 2.4 Hz, 3H, Hf),
1.19−1.09 (m, 3H, Hhexyl), 1.05−0.98 (m, 1H, Hhexyl). 13C-NMR
(150.95 MHz, DMSO-d6) δ 181.0 (C2), 179.4 (C4), 139.6 (C3′),
136.7 (Carom.), 132.9 (Carom.), 130.2 (CHarom.), 129.2 (CHar-
om.), 126.1 (CHarom.), 125.9 (C5′), 125.5 (CHarom.), 111.8 (C3),
107.2 (C4′), 97.9 (Cd), 96.5 (Ca), 95.4 (C1), 82.1 (Cc), 81.8 (Cc),
78.3 (Cb), 77.6 (Cb), 33.6 (Ce), 30.8 (C9), 30.0 (Chexyl), 29.4
(Chexyl), 27.1 (Chexyl), 27.0 (Chexyl), 26.1 (Chexyl), 22.8 (Cf),
22.2 (Cf), 17.8 (Cg). Elemental analysis found: C, 61.59; H, 5,77; N,
5.01; O, 9.09. Calcd for C29H32N2O3Ru(H2O)0.25: C, 61.85; H, 5.82;
N, 4.98; O, 9.24%.
1
Yield: 186 mg yellow/orange powder (0.39 mmol, 78%). H-NMR
(600.25 MHz, MeOD-d4) δ 8.36 (d, J = 2.2 Hz, 1H, H3′), 8.11−8.07
(m, 1H, Harom.), 7.66−7.60 (m, 3H, Harom.), 6.72 (d, J = 2.6 Hz,
1H, H5′), 6.37 (dd, J = 2.4, 2.4 Hz, 1H, H5′), 5.97 (d, J = 5.9 Hz, 1H,
Hc), 5.90 (d, J = 5.9 Hz, 1H, Hc), 5.64 (d, J = 5.9 Hz, 1H, Hb), 5.59
(d, J = 5.9 Hz, 1H, Hb), 5.30 (s, 1H, H4), 2.86 (hept, J = 6.8 Hz, 1H,
He), 2.32 (s, 3H, Hg), 1.32 (d, J = 6.9 Hz, 6H, Hf). 13C-NMR
(150.95 MHz, MeOD-d4) δ 187.5 (C2), 185.5 (C4), 141.8 (C3′),
138.2 (Carom.), 133.9 (Carom.), 132.9 (CHarom.), 131.3 (CHar-
om.), 128.2 (C5′), 128.1 (CHarom.), 127.0 (CHarom.), 109.0 (C4′),
101.0 (Ca), 99.0 (Cd), 98.1 (C3), 95.3 (C1), 83.5 (Cc), 83.1 (Cc),
80.1 (Cb), 80.0 (Cb), 32.6 (Ce), 23.0 (Cf), 22.9 (Cf), 18.4 (Cg).
Elemental analysis found: C, 57.08; H, 4.57; N, 5.88; O, 10.78. Calcd
for C23H22N2O3Ru(H2O)0.4: C, 57.23; H, 4.76; N, 5.80; O, 11.27%.
[3-Methyl-4-oxo-(1H-κN2-pyrazol-1-yl)-1,4-dihydronaphtalene-
1,2-bis(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)] (2a). The reac-
tion was performed according to the general procedure using
[RuCl2(p-cymene)]2 (150 mg, 0.24 mmol), 1H-pyrazole (34 mg,
0.50 mmol), 2 (94 mg, 0.50 mmol), and NEt3 (201 μL, 146 mg, 1.44
mmol). The mixture was stirred at 60 °C for 15 min under microwave
irradiation. Flash chromatography with EtOAc/n-hexane/NEt3 (85/
[3-(3-methylbut-2-en-1-yl)-4-oxo-(1H-κN2-pyrazol-1-yl)-1,4-dihy-
dronaphtalene-1,2-bis(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)]
(5a). The reaction was performed according to the general procedure
using [RuCl2(p-cymene)]2 (150 mg, 0.24 mmol), 1H-pyrazole (31
mg, 0.46 mmol), 5 (111 mg, 0.46 mmol), and NEt3 (201 μL, 146 mg,
1.44 mmol). The mixture was stirred at 50 °C for 15 min under
microwave irradiation. Flash chromatography with EtOAc/n-hexane/
NEt3 (70/28/2). Yield: 142 mg of yellow solid (0.26 mmol, 57%).
1H-NMR (600.25 MHz, DMSO-d6) δ 8.41 (d, J = 1.5 Hz, 1H, H3′),
1
10/5). Yield: 180 mg of yellow solid (0.37 mmol, 77%). H-NMR
(500.10 MHz, DMSO-d6) δ 8.41 (d, J = 2.1 Hz, 1H, H3′), 7.96−7.90
(m, 1H, Harom.), 7.55−7.49 (m, 2H, Harom.), 7.49−7.43 (m, 1H,
Harom.), 6.67 (d, J = 2.5 Hz, 1H, H5′), 6.31 (dd, J = 2.3, 2.3 Hz, 1H,
H4′), 6.05 (d, J = 5.8 Hz, 1H, Hc), 5.98 (d, J = 5.8 Hz, 1H, Hc), 5.67
(d, J = 5.9 Hz, 1H, Hb), 5.59 (d, J = 5.8 Hz, 1H, Hb), 2.77 (hept, J =
6.9 Hz, 1H, He), 2.25 (s, 3H, Hg), 1.59 (s, 3H, H9), 1.24 (dd, J = 7.0,
1.6 Hz, 6H, Hf). 13C-NMR (150.95 MHz, MeOD-d4) δ 183.9 (C2),
183.6 (C4), 141.5 (C3‘), 137.8 (Carom.), 134.1 (Carom.), 132.3
(Carom.), 131.2 (Carom.), 127.9 (C5′), 127.7 (Carom.), 127.1
(Carom.), 108.7 (C4′), 105.6 (C3), 101.0 (Cd), 98.7 (Ca), 94.8
(C1), 83.3 (Cc), 83.1 (Cc), 80.2 (Cb), 80.1 (Cb), 32.7 (Ce), 23.0
(Cf), 22.8 (Cf), 18.3 (Cg), 8.1 (C9). Elemental analysis found: C,
58.19; H, 4.95; N, 5.84; O, 10.05. Calcd for C24H24N2O3Ru(H2O)0.2:
C, 58.45; H, 4.99; N, 5.68; O, 10.38%.
7.96−7.90 (m, 1H, Harom.), 7.55−7.49 (m, 2H, Harom.), 7.48−7.43
(m, 1H, Harom.), 6.66 (d, J = 2.4 Hz, 1H, H5′), 6.31 (dd, J = 2.3, 2.3
Hz, 1H, H4′), 6.03 (d, J = 5.8 Hz, 1H, Hc), 5.96 (d, J = 5.9 Hz, 1H,
Hc), 5.65 (d, J = 5.9 Hz, 1H, Hb), 5.58 (d, J = 5.8 Hz, 1H, Hb),
5.07−5.02 (m, 1H, H10), 2.91−2.86 (m, 1H, H9), 2.82−2.72 (m,
2H, He and H9), 2.24 (s, 3H, Hg), 1.58 (s, 6H, H12), 1.54 (s, 3H,
H12) 1.24 (d, J = 1.4 Hz, 3H, Hf), 1.23 (d, J = 1.5 Hz, 3H, Hf). 13C-
NMR (150.95 MHz, DMSO-d6) δ 180.5 (C2), 179.6 (C4), 139.7
(C3′), 136.8 (Carom.), 132.7 (Carom.), 130.4 (CHarom.), 129.3
(CHarom.), 128.3 (C11), 126.3 (CHarom.), 126.1 (C5′), 125.3
(CHarom.), 124.4 (C10), 107.2 (C4′), 106.6 (C3), 97.8 (Cd), 96.9
(Ca), 95.3 (C1), 82.2 (Cc), 81.8 (Cc), 78.1 (Cb), 77.6 (Cb), 30.8
(Ce), 25.5 (C12), 22.7 (Cf), 22.2 (Cf), 21.8 (C9), 17.7 (Cg), 17.6
(C12). Elemental analysis found: C, 61.11; H, 5.48; N, 5.24; O, 9.03.
Calcd for C28H30N2O3Ru(H2O)0.2: C, 61.46; H, 5.60; N, 5.11; O,
9.36%.
[3-Ethyl-4-oxo-(1H-κN2-pyrazol-1-yl)-1,4-dihydronaphtalene-
1,2-bis(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)] (3a). The reac-
tion was performed according to the general procedure using
[RuCl2(p-cymene)]2 (120 mg, 0.20 mmol), 1H-pyrazole (25 mg,
0.37 mmol), 3 (75 mg, 0.37 mmol), and NEt3 (164 μL, 119 mg, 1.18
mmol). The mixture was stirred at 50 °C for 15 min under microwave
irradiation. Flash chromatography with EtOAc/n-hexane/NEt3 (85/
[3-Chloro-4-oxo-(1H-κN2-pyrazol-1-yl)-1,4-dihydronaphtalene-
1,2-bis(olato)-κO1-κO2)(η6-p-cymene)ruthenium(II)] (6a). The reac-
tion was performed according to the general procedure using
[RuCl2(p-cymene)]2 (77 mg, 0.13 mmol), 1H-pyrazole (16 mg,
0.24 mmol), 6 (50 mg, 0.24 mmol), and NEt3 (106 μL, 77 mg, 0.76
mmol). The mixture was stirred at 60 °C for 15 min under microwave
irradiation. Flash chromatography with EtOAc/n-hexane/NEt3 (90/
1
10/5). Yield: 106 mg of yellow solid (0.21 mmol, 57%). H-NMR
(600.25 MHz, MeOD-d4) δ 8.33 (d, J = 2.8 Hz, 1H, H3′), 8.11−8.07
(m, 1H, Harom.), 7.62−7.57 (m, 3H, Harom.), 6.68 (d, J = 2.4 Hz,
1H, H5′), 6.34 (dd, J = 2.4, 2.4 Hz, 1H, H4′), 5.97 (d, J = 6.5 Hz, 1H,
Hc), 5.87 (d, J = 6.3 Hz, 1H, Hc), 5.62−5.59 (m, 2H, Hb), 2.87
(hept, J = 6.9 Hz, 1H, He), 2.41−2.34 (m, 1H, H9), 2.33 (s, 3H, Hg),
2.32−2.25 (m, 1H, H9), 1.33 (d, J = 6.9 Hz, 6H, Hf), 0.88 (t, J = 7.4
Hz, 3H, H10). 13C-NMR (150.95 MHz, MeOD-d4) δ 183.5 (C2),
183.1 (C4), 141.4 (C3′), 137.7 (Carom.), 134.4 (Carom.), 132.2
1
5/5). Yield: 77 mg of yellow/orange powder (0.15 mmol, 63%). H-
NMR (600.25 MHz, MeOD-d4) δ 8.40 (d, J = 2.1 Hz, 1H, H3′),
8.16−8.12 (m, 1H, Harom.), 7.68−7.60 (m, 3H, Harom.), 6.74 (d, J
= 2.6 Hz, 1H, H5′), 6.38 (dd, J = 2.4, 2.4 Hz, 1H, H4′), 6.03 (d, J =
5.9 Hz, 1H, Hc), 5.93 (d, J = 5.9 Hz, 1H, Hc), 5.68 (d, J = 6.0 Hz,
1H, Hb), 5.66 (d, J = 6.0 Hz, 1H, Hb), 2.89 (hept, J = 6.9 Hz, 1H,
9808
Inorg. Chem. 2021, 60, 9805−9819