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WANG ET AL.
4.2.4 | Synthesis of [Ru(η6‐p‐cymene)(L4)
DMSO‐d6, δ, ppm): 169.31, 156.95, 151.50, 140.89, 133.09,
131.74, 129.28(3C), 127.02, 135.01, 123.86, 123.01, 122.22,
117.64, 101.83, 100.60, 87.20, 86.26, 81.71, 80.27, 30.93,
22.65, 22.35, 19.7. ESI‐MS (+ mode, in MeOH): m/z 552
[M − Cl]+.
Cl]Cl (4)
Compound 4 was prepared analogously by following the
method and conditions described for 1. Red powders were
obtained. Yield: 29.3%. IR (KBr, ν, cm−1): 3446 (N―H),
1680 (C¼O), 1608, 1533 (C¼N), 586, 519 (Ru―N). Anal.
Calcd for C25H24Cl3N3ORuS (%): C 48.28, H 3.89, N 6.76,
4.2.2 | Synthesis of [Ru(η6‐p‐cymene)(L2)
Cl]Cl (2)
1
S 5.16. Found (%): C 47.93, H 3.74, N 6.61, S 5.13. H
NMR (400 MHz, DMSO‐d6, δ, ppm): 9.31 (d, J = 3.8 Hz,
1H, Ar―H), 8.28–8.05 (m, 5H, Ar―H), 7.64 (d, J =
8.3 Hz, 2H, Ar―H), 7.55 (t, J = 5.6 Hz, 1H, Ar―H), 6.65
(d, J = 5.5 Hz, 1H, ―C6H4―), 6.11 (d, J = 5.5 Hz, 1H,
―C6H4―), 5.97 (d, J = 5.5 Hz, 2H, ―C6H4―), 2.46 (m,
1H, CH3C6H4CH(CH3)2), 2.25 (s, 3H, CH3C6H4CH(CH3)2),
0.91 (d, J = 6.6 Hz, 3H, CH3C6H4CH(CH3)2), 0.86 (d, J =
6.6 Hz, 3H, CH3C6H4CH(CH3)2). 13C NMR (150 MHz,
DMSO‐d6, δ, ppm): 170.67, 155.76, 152.07, 147.46, 146.16,
140.08, 136.78, 130.96(2C), 129.02(2C), 125.87, 124.06,
123.84, 121.86, 101.37, 100.57, 86.99, 86.29, 81.32, 79.93,
30.92, 22.39, 22.30, 19.54. ESI‐MS (+ mode, in MeOH):
m/z 586 [M − Cl]+.
Compound 2 was prepared analogously by following the
method and conditions described for 1. Red powders were
obtained. Yield: 23.1%. IR (KBr, ν, cm−1): 3451 (N―H),
1678 (C¼O), 1604, 1536 (C¼N), 598, 522 (Ru―N) cm‐1.
Anal. Calcd for C26H27Cl2N3ORuS (%): C 51.91, H 4.52, N
6.99, S 5.33. Found (%): C 51.74, H 4.47, N 7.14, S 5.42. 1H
NMR (400 MHz, DMSO‐d6, δ, ppm): 9.35 (d, J = 5.1 Hz,
1H, Ar―H), 8.27–8.17 (m, 3H, Ar―H), 8.01(d, J = 8.1 Hz,
2H, Ar―H), 7.61 (m, 1H, Ar―H), 7.41(d, J = 8.1 Hz, 2H,
Ar―H), 6.65 (d, J = 5.2 Hz, 1H, ―C6H4―), 6.18 (d, J =
5.2 Hz, 1H, ―C6H4―), 6.02 (d, J = 5.2 Hz, 2H,
―C6H4―), 2.47 (m, 1H, CH3C6H4CH(CH3)2), 2.44(s, 3H,
Ar―CH3), 2.27(s, 3H, CH3C6H4CH(CH3)2), 0.92 (d, J =
6.8 Hz, 3H, CH3C6H4CH(CH3)2), 0.87 (d, J = 6.8 Hz, 3H,
CH3C6H4CH(CH3)2). 13C NMR (150 MHz, DMSO‐d6, δ,
ppm): 165.91, 156.99, 151.45, 143.67, 142.31, 140.98,
129.93(2C), 129.30(2C), 127.10, 124.40, 123.29, 122.15,
101.95, 100.56, 87.22, 86.26, 81.74, 80.23, 30.91, 22.67,
22.35, 21.98, 19.78. ESI‐MS (+ mode, in MeOH): m/z 566
[M − Cl]+.
4.2.5 | Synthesis of [Ru(η6‐p‐cymene)(L5)
Cl]Cl (5)
Compound 5 was prepared analogously by following the
method and conditions described for 1. Red powders were
obtained. Yield: 31.2%. IR (KBr, ν, cm−1): 3462 (N―H),
1686 (C¼O), 1610, 1537 (C¼N), 593, 516 (Ru―N). Anal.
Calcd for C25H24Cl2BrN3ORuS (%): C 45.06, H 3.63, N
6.31, S 4.81. Found (%): C 44.86, H 3.39, N 6.34, S 4.62. 1H
NMR (400 MHz, DMSO‐d6, δ, ppm): 9.31 (d, J = 5.4 Hz,
1H, Ar―H), 8.30–8.02 (m, 3H, Ar―H), 7.97–7.91 (m, 4H,
Ar―H), 7.54 (t, J = 5.6 Hz, 1H, Ar―H), 6.64 (d, J =
5.2 Hz, 1H, ―C6H4―), 6.11 (d, J = 5.2 Hz, 1H,
―C6H4―), 5.96 (d, J = 5.2 Hz, 2H, ―C6H4―), 2.46 (m,
1H, CH3C6H4CH(CH3)2), 2.25 (s, 3H, CH3C6H4CH(CH3)2),
0.92 (d, J = 6.8 Hz, 3H, CH3C6H4CH(CH3)2), 0.88 (d, J =
6.8 Hz, 3H, CH3C6H4CH(CH3)2). 13C NMR (150 MHz,
DMSO‐d6, δ, ppm): 169.38, 156.64, 151.81, 146.38, 140.66,
138.52, 132.16(2C), 131.26(2C), 127.02, 126.62, 126.01,
123.94, 122.79, 101.61, 101.24, 89.22, 86.24, 81.63, 80.15,
30.94, 22.57, 22.40, 19.78. ESI‐MS (+ mode, in MeOH):
m/z 629 [M − Cl]+.
4.2.3 | Synthesis of [Ru(η6‐p‐cymene)(L3)
Cl]Cl (3)
Compound 3 was prepared analogously by following the
method and conditions described for 1. Red powders were
obtained. Yield: 18.9%. IR (KBr, ν, cm−1): 3451 (N―H),
1681 (C¼O), 1609, 1533 (C¼N), 584, 517 (Ru―N). Anal.
Calcd for C25H24Cl2FN3ORuS (%): C 49.59, H 4.00, N
6.94, S 5.29. Found (%): C 49.42, H 4.19, N 6.74, S 5.15.
1H NMR (400 MHz, DMSO‐d6, δ, ppm): 9.32 (d, J =
5.6 Hz, 1H, Ar―H), 8.22–8.18 (m, 4H, Ar―H), 8.11 (d,
J = 7.7 Hz, 1H,Ar―H), 7.56 (t, J = 5.6 Hz, 1H, Ar―H),
7.40 (t, J = 8.7 Hz, 2H, Ar―H), 6.68 (d, J = 5.8 Hz, 1H,
―C6H4―), 6.13 (d, J = 5.8 Hz, 1H, ―C6H4―), 5.98 (d,
J
=
6.1 Hz, 2H, ―C6H4―), 2.47 (m, 1H,
CH3C6H4CH(CH3)2), 2.26 (s, 3H, CH3C6H4CH(CH3)2),
0.92 (d, J = 6.9 Hz, 3H, CH3C6H4CH(CH3)2), 0.87 (d, J =
6.9 Hz, 3H, CH3C6H4CH(CH3)2). 13C NMR (150 MHz,
DMSO‐d6, δ, ppm): 165.76, 164.13, 162.13, 156.84,
151.59, 146.59, 140.70, 132.26, 127.00, 124.87, 122.80,
116.15, 114.29, 111.19, 106.77, 101.50, 100.59, 87.17,
86.23, 81.61, 80.14, 30.99, 22.63, 22.34, 19.76. ESI‐MS
(+ mode, in MeOH): m/z 570 [M − Cl]+.
4.2.6 | Synthesis of [Ru(η6‐p‐cymene)(L6)
Cl]Cl (6)
Compound 6 was prepared analogously by following the
method and conditions described for 1. Red powders were
obtained. Yield: 34.6%. IR (KBr, ν, cm−1): 3442 (N―H),
1676 (C¼O), 1609, 1529 (C¼N), 588, 519 (Ru―N). Anal.