2.2. General Procedure for the Synthesis of Zeise’s Salt Derivatives
Zeise’s salt monohydrate (0.20 mmol) dissolved in 8 mL of dry ethanol (EtOH), which was degassed (three cycles of freeze-pump-thaw), and stirred at room temperature under protection from light and under an argon atmosphere. Then, 0.24 mmol of the respective ligand (1.2 eq.), solved in about 2 mL of dry and degassed EtOH, was added drop by drop with a syringe. Next, the mixture underwent stirring at 48 °C for 3.5 h, followed by cooling to room temperature. The solution was filtered and evaporated to dryness. The recrystallization of the crude product from EtOH/diethyl ether or EtOH/diisopropyl ether afforded pure solid products.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-3-fluorobenzoate]platinate(II) (3-F-ASA-Prop-PtCl3). Yellow powder; yield: 71%. 1H NMR (400 MHz, acetone-d6): δ = 7.91 (ddd, 3J = 7.9 Hz, 4J = 1.5 Hz, 5JH-F = 1.5 Hz, 1H, Ar-H6), 7.54 (ddd, 3JH-F = 9.9 Hz, 3J = 8.3 Hz, 4J = 1.6 Hz, 1H, Ar-H4), 7.43 (ddd, 3J = 8.1 Hz, 3J = 8.1 Hz, 4JH-F = 5.1 Hz, 1H, Ar-H5), 4.99 (dddd, 2JH-Pt = 59 Hz, 3J = 12.6 Hz, 3J = 9.0 Hz, 3J = 6.5 Hz, 3J = 6.5 Hz, 1H, -CH=), 4.91 (dd, 3JH-Pt = 35 Hz, 2J = 11.9 Hz, 3J = 5.8 Hz, 1H, -OCHαHβ-), 4.50 (dd, 3JH-Pt = 38 Hz, 2J = 11.9 Hz, 3J = 7.3 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 74 Hz, 3J = 12.4 Hz, 2J = 1.2 Hz, 1H, =CH2, trans), 4.30 (d, 2JH-Pt = 59 Hz, 3J = 7.9 Hz, 2J = 1.0 Hz, 1H, =CH2,cis), 2.40 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 168.04 (-(C=O)-CH3), 163.31 (d, 4JC-F = 3.1 Hz, Ar-(C=O)), 154.94 (d, 1JC-F = 247.1 Hz, C3), 138.55 (d, 2JC-F = 14.8 Hz, C2), 126.95 (d, 4JC-F = 3.6 Hz, C6), 126.79 (d, 3JC-F = 7.7 Hz, C5), 126.00 (C1), 120.48 (d, 2JC-F = 19.1 Hz, C4), 76.43 (C2′), 64.85 (C1′), 64.12 (C3′), 19.85 (-OAc). HR-ESI-MS (m/z): 539.9333 ([M-K]−, calcd for C12H11Cl3FO4Pt: 539.9320). CE-purity: 95.2%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-4-fluorobenzoate]platinate(II) (4-F-ASA-Prop-PtCl3). Yellow powder; yield: 70%. 1H NMR (400 MHz, acetone-d6): δ = 8.19 (dd, 3J = 8.8 Hz, 4JH-F = 6.5 Hz, 1H, Ar-H6), 7.21 (ddd, 3J = 8.8 Hz, 3JH-F = 8.1 Hz, 4J = 2.6 Hz, 1H, Ar-H5), 7.07 (dd, 3JH-F = 9.3 Hz, 4J = 2.6 Hz, 1H, Ar-H3), 4.99 (dddd, 2JH-Pt = 61 Hz, 3J = 12.9 Hz, 3J = 7.6 Hz, 3J = 7.6 Hz, 3J = 5.7 Hz, 1H, -CH = ), 4.88 (dd, 3JH-Pt = 30 Hz, 2J = 11.9 Hz, 3J = 5.7 Hz, 1H, -OCHαHβ-), 4.48 (dd, 2J = 12.0 Hz, 3J = 7.5 Hz, 1H, -OCHαHβ-), 4.33 (dd, 2JH-Pt = 72 Hz, 3J = 12.7 Hz, 2J = 1.3 Hz, 1H, =CH2, trans), 4.30 (ddd, 2JH-Pt = 60 Hz, 3J = 7.9 Hz, 2J = 1.3 Hz, 4J = 0.5 Hz, 1H, =CH2, cis), 2.34 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.54 (-(C=O)-CH3), 166.11 (d, 1JC-F = 253.4 Hz, C4), 164.12 (Ar-(C=O)), 153.42 (d, 3JC-F = 11.7 Hz, C2), 134.81 (d, 3JC-F = 10.3 Hz, C6), 121.31 (d, 4JC-F = 3.7 Hz, C1), 113.96 (d, 2JC-F = 21.7 Hz, C5), 112.50 (d, 2JC-F = 24.6 Hz, C3), 77.44 (C3′), 65.48 (C1′), 65.02 (C2′), 21.18 (-OAc). HR-ESI-MS (m/z): 537.9390 ([M-K]−, calcd for C12H11Cl3FO4Pt: 537.9349). CE-purity: 97.1%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-5-fluorobenzoate]platinate(II) (5-F-ASA-Prop-PtCl3). Yellow powder; yield: 75%. 1H NMR (400 MHz, acetone-d6): δ = 7.81 (dd, 3JH-F = 9.0 Hz, 4J = 3.2 Hz, 1H, Ar-H6), 7.44 (ddd, 3J = 8.9 Hz, 3JH-F = 7.7 Hz, 4J = 3.2 Hz, 1H, Ar-H4), 7.25 (dd, 3J = 8.9 Hz, 4JH-F = 4.7 Hz, 1H, Ar-H3), 4.99 (dddd, 2JH-Pt = 68 Hz, 3J = 12.7 Hz, 3J = 7.6 Hz, 3J = 7.6 Hz, 3J = 5.6 Hz, 1H, -CH=), 4.90 (dd, 3JH-Pt = 34 Hz, 2J = 11.9 Hz, 3J = 5.7 Hz, 1H, -OCHαHβ-), 4.50 (dd, 3JH-Pt = 40 Hz, 2J = 11.9 Hz, 3J = 7.5 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 74 Hz, 3J = 12.6 Hz, 2J = 1.2 Hz, 1H, =CH2, trans), 4.31 (dd, 2JH-Pt = 60 Hz, 3J = 7.9 Hz, 2J = 0.9 Hz, 1H, =CH2, cis), 2.33 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.92 (-(C=O)-CH3), 163.97 (d, 4JC-F = 2.3 Hz, Ar-(C=O)), 160.50 (d, 1JC-F = 244.1 Hz, C5), 147.69 (d, 4JC-F = 2.9 Hz, C2), 126.80 (d, 3JC-F = 8.5 Hz, C3), 126.17 (d, 3JC-F = 7.4 Hz, C1), 121.37 (d, 2JC-F = 23.3 Hz, C4), 118.67 (d, 2JC-F = 25.4 Hz, C6), 77.17 (C3′), 65.76 (C1′), 65.13 (C2′), 21.15 (-OAc). HR-ESI-MS (m/z): 538.9330 ([M-K]−, calcd for C12H11Cl3FO4Pt: 538.9299). CE-purity: 95.8%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-6-fluorobenzoate]platinate(II) (6-F-ASA-Prop-PtCl3). Light yellow crystals; yield: 79%. 1H NMR (400 MHz, acetone-d6): δ = 7.60 (ddd, 3J = 8.4 Hz, 3J = 8.4 Hz, 4JH-F = 6.2 Hz, 1H, Ar-H4), 7.18 (ddd, 3JH-F = 9.6 Hz, 3J = 8.5 Hz, 4J = 1.0 Hz, 1H, Ar-H5), 7.09 (ddd, 3J = 8.2 Hz, 4J = 1.0 Hz, 5JH-F = 1.0 Hz, 1H, Ar-H3), 5.11-4.80 (m, 2H, -CH= and -OCHαHβ-), 4.65-4.53 (m, 3JH-Pt = 41 Hz, 1H, -OCHαHβ-), 4.46-4.21 (m, 2JH-Pt = 70 Hz, 2H, =CH2), 2.31 (s, 3H, -CH3). 13C NMR (101 MHz, acetone-d6): δ = 169.28 (-(C=O)-CH3), 162.66 (Ar-(C=O)), 161.21 (d, 1JC-F = 254.1 Hz, C6), 150.67 (d, 3JC-F = 5.2 Hz, C2), 133.37 (d, 3JC-F = 10.3 Hz, C4), 120.36 (d, 4JC-F = 3.6 Hz, C3), 116.64 (d, 2JC-F = 17.6 Hz, C1), 114.38 (d, 2JC-F = 21.9 Hz, C5), 76.51 (C2′), 65.79 (C1′), 65.27 (C3′), 21.03 (-OAc). HR-ESI-MS (m/z): 538.9330 ([M-K]−, calcd for C12H11Cl3FO4Pt: 538.9299). CE-purity: 95.5%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-3-fluorobenzoate]platinate(II) (3-F-ASA-But-PtCl3). Yellow powder; yield: 29%. 1H NMR (400 MHz, acetone-d6): δ = 7.90 (ddd, 3J = 7.9 Hz, 4J = 1.5 Hz, 5JH-F = 1.5 Hz, 1H, Ar-H6), 7.53 (ddd, 3JH-F = 9.9 Hz, 3J = 8.3 Hz, 4J = 1.6 Hz, 1H, Ar-H4), 7.43 (ddd, 3J = 8.1 Hz, 3J = 8.1 Hz, 4JH-F = 5.1 Hz, 1H, Ar-H5), 5.00 (dddd, 2JH-Pt = 66 Hz, 3J = 13.7 Hz, 3J = 7.9 Hz, 3J = 6.2 Hz, 3J = 6.2 Hz, 1H, -CH=), 4.74-4.61 (m, 2H, -OCH2-), 4.36-4.11 (m, 2JH-Pt = 60 Hz, 2H, =CH2), 2.58 (ddt, 2J = 14.2 Hz, 3J = 8.1 Hz, 3J = 6.0 Hz, 1H, -CHαHβ-), 2.09-2.00 (m, 1H, -CHαHβ-), 2.37 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 168.83 (-(C=O)-CH3), 164.32 (d, 4JC-F = 3.6 Hz, Ar-(C=O)), 155.84 (d, 1JC-F = 247.1 Hz, C3), 139.45 (d, 2JC-F = 14.5 Hz, C2), 127.73 (d, 4JC-F = 3.8 Hz, C6), 127.71 (d, 3JC-F = 7.5 Hz, C5), 126.96 (C1), 121.31 (d, 2JC-F = 19.6 Hz, C4), 84.00 (C3′), 65.96 (C4′), 65.27 (C1′), 33.25 (C2′), 20.61 (-OAc). HR-ESI-MS (m/z): 534.9825 ([M-K-Cl + OH]−, calcd for C13H14Cl2FO5Pt: 534.9846), 552.9475 ([M-K]−, calcd for C13H13Cl3FO4Pt: 552.9455). CE-purity: 97.8%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-4-fluorobenzoate]platinate(II) (4-F-ASA-But-PtCl3). Yellow powder; yield: 85%. 1H NMR (400 MHz, acetone-d6): δ = 8.20 (dd, 3J = 8.9 Hz, 4JH-F = 6.5 Hz, 1H, Ar-H6), 7.19 (ddd, 3J = 8.9 Hz, 3JH-F = 8.1 Hz, 4J = 2.6 Hz, 1H, Ar-H5), 7.05 (dd, 3JH-F = 9.3 Hz, 4J = 2.6 Hz, 1H, Ar-H3), 5.00 (dddd, 2JH-Pt = 66 Hz, 3J = 12.0 Hz, 3J = 9.1 Hz, 3J = 8.0 Hz, 3J = 6.1 Hz, 1H, -CH=), 4.71-4.58 (m, 2H, -OCH2-), 4.37-4.11 (m, 2JH-Pt = 60 Hz, 2H, =CH2), 2.57 (ddt, 2J = 14.2 Hz, 3J = 8.1 Hz, 3J = 6.1 Hz, 1H, -CHαHβ-), 2.09-1.98 (m, 1H, -CHαHβ-), 2.31 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.46 (-(C=O)-CH3), 166.06 (d, 1JC-F = 252.9 Hz, C4), 164.24 (Ar-(C=O)), 153.47 (d, 3JC-F = 12.3 Hz, C2), 134.76 (d, 3JC-F = 10.6 Hz, C6), 121.35 (d, 4JC-F = 3.7 Hz, C1), 113.96 (d, 2JC-F = 21.3 Hz, C5), 112.48 (d, 2JC-F = 24.1 Hz, C3), 84.26 (C3′), 65.96 (C4′), 64.97 (C1′), 33.25 (C2′), 21.07 (-OAc). HR-ESI-MS (m/z): 552.9525 ([M-K]−, calcd for C13H13Cl3FO4Pt: 552.9505). CE-purity: 96.9%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-5-fluorobenzoate]platinate(II) (5-F-ASA-But-PtCl3). Yellow powder; yield: 51%. 1H NMR (400 MHz, acetone-d6): δ = 7.78 (dd, 3JH-F = 8.9 Hz, 4J = 3.2 Hz, 1H, Ar-H6), 7.43 (ddd, 3J = 9.0 Hz, 3JH-F = 7.8 Hz, 4J = 3.2 Hz, 1H, Ar-H4), 7.25 (dd, 3J = 8.9 Hz, 4JH-F = 4.7 Hz, 1H, Ar-H3), 5.00 (dddd, 2JH-Pt = 64 Hz, 3J = 13.7 Hz, 3J = 8.0 Hz, 3J = 8.0 Hz, 3J = 6.1 Hz, 1H, -CH=), 4.73-4.62 (m, 2H, -OCH2-), 4.35-4.12 (m, 2JH-Pt = 63 Hz, 2H, =CH2), 2.56 (ddt, 2J = 14.3 Hz, 3J = 8.1 Hz, 3J = 6.1 Hz, 1H, -CHαHβ-), 2.09-1.99 (m, 1H, -CHαHβ-), 2.30 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.86 (-(C=O)-CH3), 164.10 (d, 4JC-F = 2.2 Hz, Ar-(C=O)), 160.50 (d, 1JC-F = 245.0 Hz, C5), 147.72 (d, 4JC-F = 2.9 Hz, C2), 126.81 (d, 3JC-F = 8.5 Hz, C3), 126.23 (d, 3JC-F = 7.7 Hz, C1), 121.32 (d, 2JC-F = 23.5 Hz, C4), 118.53 (d, 2JC-F = 25.5 Hz, C6), 83.90 (C3′), 65.91 (C4′), 65.33 (C1′), 33.21 (C2′), 21.04 (-OAc). HR-ESI-MS (m/z): 552.9474 ([M-K]−, calcd for C13H13Cl3FO4Pt: 552.9455). CE-purity: 98.0%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-6-fluorobenzoate]platinate(II) (6-F-ASA-But-PtCl3). Yellow powder; yield: 84%. 1H NMR (400 MHz, acetone-d6): δ = 7.60 (ddd, 3J = 8.4 Hz, 3J = 8.4 Hz, 4JH-F = 6.2 Hz, 1H, Ar-H4), 7.18 (ddd, 3JH-F = 9.5 Hz, 3J = 8.5 Hz, 4J = 1.0 Hz, 1H, Ar-H5), 7.09 (ddd, 3J = 8.3 Hz, 4J = 1.0 Hz, 5JH-F = 1.0 Hz, 1H, Ar-H3), 4.98 (dddd, 2JH-Pt = 64 Hz, 3J = 12.0 Hz, 3J = 8.9 Hz, 3J = 7.7 Hz, 3J = 6.6 Hz, 1H, -CH=), 4.68 (dd, 3J = 7.3 Hz, 3J = 6.2 Hz, 2H, -OCH2-), 4.35-4.13 (m, 2JH-Pt = 62 Hz, 2H, =CH2), 2.57 (ddt, 2J = 14.0 Hz, 3J = 7.8 Hz, 3J = 6.2 Hz, 1H, -CHαHβ-), 2.09-2.00 (m, 1H, -CHαHβ-), 2.29 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.24 (-(C=O)-CH3), 162.90 (Ar-(C=O)), 161.21 (d, 1JC-F = 254.0 Hz, C6), 150.74 (d, 3JC-F = 5.2 Hz, C2), 133.34 (d, 3JC-F = 10.2 Hz, C4), 120.38 (d, 4JC-F = 3.5 Hz, C3), 116.72 (d, 2JC-F = 17.6 Hz, C1), 114.39 (d, 2JC-F = 22.3 Hz, C5), 83.81 (C3′), 66.10 (C4′), 65.54 (C1′), 33.41 (C2′), 20.96 (-OAc). HR-ESI-MS (m/z): 552.9489 ([M-K]−, calcd for C13H13Cl3FO4Pt: 552.9455). CE-purity: 96.7%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-3-chlorobenzoate]platinate(II) (3-Cl-ASA-Prop-PtCl3). Yellow powder; yield: 76%. 1H NMR (400 MHz, acetone-d6): δ = 8.07 (dd, 3J = 7.9 Hz, 4J = 1.6 Hz, 1H, Ar-H6), 7.78 (dd, 3J = 8.0 Hz, 4J = 1.6 Hz, 1H, Ar-H4), 7.44 (dd, 3J = 8.0 Hz, 3J = 8.0 Hz, 1H, Ar-H5), 4.99 (dddd, 2JH-Pt = 61 Hz, 3J = 12.8 Hz, 3J = 7.5 Hz, 3J = 5.8 Hz, 3J = 5.8 Hz, 1H, -CH=), 4.90 (dd, 3JH-Pt = 26 Hz, 2J = 11.9 Hz, 3J = 5.8 Hz, 1H, -OCHαHβ-), 4.49 (dd, 3JH-Pt = 32 Hz, 2J = 11.9 Hz, 3J = 7.3 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 59 Hz, 3J = 12.6 Hz, 2J = 1.3 Hz, 1H, =CH2, trans), 4.30 (d, 2JH-Pt = 59 Hz, 3J = 7.9 Hz, 2J = 1.1 Hz, 1H, =CH2, cis), 2.40 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 168.70 (-(C=O)-CH3), 164.19 (Ar-(C=O)), 147.85 (C2), 134.96 (C4), 131.35 (C6), 129.41 (C3), 127.80 (C5), 126.76 (C1), 77.34 (C2′), 66.09 (C3′), 65.79 (C1′), 20.84 (-OAc). HR-ESI-MS (m/z): 555.9045 ([M-K]−, calcd for C12H11Cl4O4Pt: 555.9024. CE-purity: 95.2%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-4-chlorobenzoate]platinate(II) (4-Cl-ASA-Prop-PtCl3). Yellow powder; yield: 88%. 1H NMR (200 MHz, acetone-d6): 8.12 (d, 3J = 8.8 Hz, 1H, Ar-H6), 7.46 (dd, 3J = 8.4 Hz, 4J = 2.2 Hz, 1H, Ar-H5), 7.32 (d, 4J = 2.2 Hz, 1H, Ar-H3), 5.05–4.93 (m, 1H, -CH=CH2), 4.93–4.84 (m, 1H, CH2-CH=), 4.53–4.44 (m, 1H, CH2-CH=), 4.36–4.27 (m, 2H, CH=CH2), 2.34 (s, 3H, -CH3). 13C NMR (101 MHz, acetone-d6): δ = 169.60 (-(C=O)-CH3), 164.20 (Ar-(C=O)), 152.33 (C2), 139.39 (C4), 133.95 (C6), 127.10 (C5), 125.19 (C3), 123.58 (C1), 77.31 (C2′), 66.10 (C1′), 65.04 (C3′), 21.07 (-OAc). HR-ESI-MS (m/z): 555.9036 ([M-K]−, calcd for C12H11Cl4O4Pt: 555.9024). CE-purity: 95.6%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-5-chlorobenzoate]platinate(II) (5-Cl-ASA-Prop-PtCl3). Yellow powder; yield: 53%. 1H NMR (400 MHz, acetone-d6): 8.13 (d, 3J = 8.4 Hz, 1H, Ar-H3), 7.47 (dd, 3J = 8.4 Hz, 4J = 2.2 Hz, 1H, Ar-H4), 7.32 (d, 3J = 2.2 Hz, 1H, Ar-H6), 5.06–4.93 (m, 1H, -CH=CH2), 4.93–4.80 (m, 1H, -CH2-CH), 4.56–4.44 (m, 1H, -CH2-CH), 4.36–4.28 (m, 2H, -CH=CH2), 2.34 (s, 3H, -CH3) δ = 8.06 (d, 4J = 2.7 Hz, 1H, Ar-H6), 7.68 (dd, 3J = 8.7 Hz, 4J = 2.7 Hz, 1H, Ar-H4), 7.25 (d, 3J = 8.6 Hz, 1H, Ar-H3), 4.99 (dddd, 2JH-Pt = 64 Hz, 3J = 12.8 Hz, 3J = 7.8 Hz, 3J = 7.5 Hz, 3J = 5.5 Hz, 1H, -CH=CH2), 4.91 (dd, 2J = 11.8 Hz, 3J = 5.6 Hz, 1H, -OCHαHβ-), 4.50 (dd, 2J = 11.9 Hz, 3J = 7.5 Hz, 1H, -OCHαHβ-), 4.35 (dd, 3J = 12.5 Hz, 2J = 1.3 Hz, 1H, =CH2, trans), 4.31 (dd, 3J = 7.8 Hz, 2J = 1.3 Hz, 1H, =CH2, cis), 2.34 (s, 3H, -CH3). 13C NMR (101 MHz, acetone-d6): δ = 169.74 (-(C=O)-CH3), 163.89 (Ar-(C=O)), 150.23 (C2), 134.45 (C4), 131.96 (C6), 131.62 (C5), 126.77 (C3), 126.25 (C1), 77.15 (C2′), 65.78 (C3′), 65.19 (C1′), 21.17 (-OAc). HR-ESI-MS (m/z): 555.8581 ([M-K]−, calcd for C12H11Cl4O4Pt: 555.9024). CE-purity: 96.1%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-6-chlorobenzoate]platinate(II) (6-Cl-ASA-Prop-PtCl3). Yellow powder; yield: 66%. 1H NMR (400 MHz, acetone-d6): δ = 7.53 (dd, 3J = 8.2 Hz, 3J = 8.2 Hz, 1H, Ar-H4), 7.42 (dd, 3J = 8.1 Hz, 4J = 1.0 Hz, 1H, Ar-H5), 7.26 (dd, 3J = 8.2 Hz, 4J = 1.1 Hz, 1H, Ar-H3), 5.09–4.88 (m, 2H, -CH= and -OCHαHβ-), 4.71–4.48 (m, 1H, -OCHαHβ-), 4.45–4.22 (m, 2H, =CH2), 2.30 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.06 (-(C=O)-CH3), 164.35 (Ar-(C=O)), 149.72 (C2), 132.16 (C4), 132.05 (C6), 128.34 (C1), 127.76 (C5), 123.10 (C3), 76.52 (C2′), 65.93 and 65.29 (C1′and C3′), 20.97 (-OAc). HR-ESI-MS (m/z): 555.9046 ([M-K]−, calcd for C12H11Cl4O4Pt: 555.9024). CE-purity: 95.1%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-3-chlorobenzoate]platinate(II) (3-Cl-ASA-But-PtCl3). Yellow powder; yield: 40%. 1H NMR (400 MHz, acetone-d6): δ = 8.06 (dd, 3J = 7.9 Hz, 4J = 1.6 Hz, 1H, Ar-H6), 7.77 (dd, 3J = 8.1 Hz, 4J = 1.6 Hz, 1H, Ar-H4), 7.43 (dd, 3J = 8.0 Hz, 3J = 8.0 Hz, 1H, Ar-H5), 5.14–4.88 (m, 2JH-Pt = 67 Hz, 1H, -CH=), 4.74–4.60 (m, 2H, -OCH2-), 4.37–4.11 (m, 2JH-Pt = 71 Hz, 2H, =CH2), 2.57 (ddt, 2J = 14.3 Hz, 3J = 8.1 Hz, 3J = 6.0 Hz, 1H, -CHαHβ-), 2.37 (s, 3H, -OAc), 2.08–1.99 (m, 1H, -CHαHβ-). 13C NMR (101 MHz, acetone-d6): δ = 168.59 (-(C=O)-CH3), 164.31 (Ar-(C=O)), 147.85 (C2), 134.89 (C4), 131.23 (C6), 129.39 (C3), 127.83 (C5), 126.78 (C1), 84.18 (C3′), 66.02 (C4′), 65.29 (C1′), 33.20 (C2′), 20.70 (-OAc). HR-ESI-MS (m/z): 569.9204 ([M-K]−, calcd for C13H13Cl4O4Pt: 569.9181). CE-purity: 100.0%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-4-chlorobenzoate]platinate(II) (4-Cl-ASA-But-PtCl3). Yellow powder; yield: 92%. 1H NMR (200 MHz, acetone-d6): 8.14 (d, 3J = 8.4 Hz, 1H, Ar-H6), 7.45 (dd, 3J = 8.4 Hz, 4J = 1.8 Hz, 1H, Ar-H5), 7.31 (d, 4J = 2.2 Hz, 1H, Ar-H3), 5.07–4.90 (m, 1H, -CH=CH2), 4.65 (t, 3J = 6.8 Hz, 2H, O-CH2-CH2), 4.26–4.20 (m, 2H, -CH=CH2), 2.65–2.48 (m, 1H, -CH2-CH2-CH), 2.32 (s, 3H, -CH3), 2.09–1.97 (m, 1H, -CH2-CH2-CH). 13C NMR (101 MHz, acetone-d6): δ = 169.52 (-(C=O)-CH3), 164.31 (Ar-(C=O)), 152.37 (C2), 139.31 (C4), 133.91 (C6), 127.12 (C5), 125.15 (C3), 123.59 (C1), 84.22 (C2′), 65.96 (C1′), 65.10 (C4′), 33.19 (C3′), 21.05 (-OAc). HR-ESI-MS (m/z): 569.9204 ([M-K]−, calcd for C13H13Cl4O4Pt: 569.9181). CE-purity: 97.8%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-5-chlorobenzoate]platinate(II) (5-Cl-ASA-But-PtCl3).
Yellow powder; yield: 58%. 1H NMR (200 MHz, acetone-d6): 8.03 (d, 4J = 2.6 Hz, 1H, Ar-H6), 7.67 (dd, 3J = 8 Hz, 4J = 2.2 Hz, 1H, Ar-H4), 7.25 (d, 3J = 8.6 Hz, 1H, Ar-H3), 5.08–4.90 (m, 1H, -CH = CH2), 4.68 (t, 3J = 6.2 Hz, 2H, O-CH2-CH2), 4.26–4.21 (m, 2H, -CH=CH2), 2.65–2.48 (m, 1H, -CH2-CH2-CH), 2.31 (s, 3H, -CH3), 2.07–1.95 (m, 1 H, -CH2-CH2-CH). 13C NMR (101 MHz, acetone-d6): δ = 169.66 (-(C=O)-CH3), 164.00 (Ar-(C=O)), 150.23 (C2), 134.41 (C4), 131.77 (C6), 131.61 (C5), 126.77 (C3), 126.28 (C1), 84.15 (C2′), 66.05 (C1′), 65.30 (C4′), 33.20 (C3′), 21.04 (-OAc). HR-ESI-MS (m/z): 569.9193 ([M-K]−, calcd for C13H13Cl4O4Pt: 569.9181). CE-purity: 97.5%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-6-chlorobenzoate]platinate(II) (6-Cl-ASA-But-PtCl3).
Yellow powder; yield: 68%. 1H NMR (200 MHz, aceton-d6): 7.57–7.39 (m, 2H, Ar-H), 7.25 (dd, 3J = 7.6 Hz, 4J = 1.6 Hz, 1H, Ar-H), 5.08–4.91 (m, 1H, -CH=CH2), 4.71 (t, 3J = 6.2 Hz, 2H, O-CH2-CH2), 4.26–4.19 (m, 2H, -CH=CH2), 2.66–2.49 (m, 1H, -CH2-CH2-CH), 2.29 (s, 3H, -CH3), 2.09–1.95 (m, 1H, -CH2-CH2-CH). 13C NMR (101 MHz, acetone-d6): δ = 169.01 (-(C=O)-CH3), 164.56 (Ar-(C=O)), 149.71 (C2), 132.10 (C4), 131.99 (C6), 128.50 (C1), 127.74 (C5), 123.09 (C3), 83.85 (C2′), 66.12 (C1′), 65.76 (C4′), 33.33 (C3′), 20.93 (-OAc). HR-ESI-MS (m/z): 569.9202 ([M-K]−, calcd for C13H13Cl4O4Pt: 569.9181). CE-purity: 95.6%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-3-methylbenzoate]platinate(II) (3-CH3-ASA-Prop-PtCl3). Yellow powder; yield: 83%. 1H NMR (400 MHz, acetone-d6): δ = 7.92 (dd, 3J = 7.9 Hz, 4J = 1.6 Hz, 1H, Ar-H6), 7.53 (d, 3J = 7.3 Hz, 1H, Ar-H4), 7.53 (dd, 3J = 7.7 Hz, 3J = 7.7 Hz, 1H, Ar-H5), 5.00 (dddd, 2JH-Pt = 63 Hz, 3J = 13.2 Hz, 3J = 7.7 Hz, 3J = 5.6 Hz, 3J = 5.6 Hz, 1H, -CH=), 4.89 (dd, 3JH-Pt = 34 Hz, 2J = 11.9 Hz, 3J = 5.5 Hz, 1H, -OCHαHβ-), 4.48 (dd, 3JH-Pt = 33 Hz, 2J = 12.0 Hz, 3J = 7.6 Hz, 1H, -OCHαHβ-), 4.35 (d, 2JH-Pt = 72 Hz, 3J = 12.8 Hz, 1H, =CH2, trans), 4.31 (d, 2JH-Pt = 58 Hz, 3J = 7.9 Hz, 1H, =CH2, cis), 2.36 (s, 3H, -OAc), 2.21 (s, 3H, -CH3). 13C NMR (101 MHz, acetone-d6): δ = 169.40 (-(C=O)-CH3), 165.17 (Ar-(C=O)), 150.13 (C2), 136.02 (C4), 133.07 (C3), 130.24 (C6), 126.42 (C5), 124.56 (C1), 77.77 (C2′), 65.30 (C3′), 65.15 (C1′), 21.04 (-OAc), 16.14 (-CH3). HR-ESI-MS (m/z): 534.9588 ([M-K]−, calcd for C13H14Cl3O4Pt: 534.9575). CE-purity: 96.7%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-4-methylbenzoate]platinate(II) (4-CH3-ASA-Prop-PtCl3). Yellow powder; yield: 75%. 1H NMR (400 MHz, acetone-d6): δ = 7.98 (d, 3J = 8.0 Hz, 1H, Ar-H6), 7.20 (dq, 3J = 8.2 Hz, 4J = 0.9 Hz, 1H, Ar-H5), 7.00 (d, 4J = 0.4 Hz, 1H, Ar-H3), 5.00 (dddd, 2JH-Pt = 62 Hz, 3J = 13.0 Hz, 3J = 7.8 Hz, 3J = 5.4 Hz, 3J = 5.4 Hz, 1H, -CH=), 4.88 (dd, 3JH-Pt = 34 Hz, 2J = 12.0 Hz, 3J = 5.5 Hz, 1H, -OCHαHβ-), 4.47 (dd, 3JH-Pt = 31 Hz, 2J = 12.0 Hz, 3J = 7.7 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 75 Hz, 3J = 12.8 Hz, 2J = 1.2 Hz, 1H, =CH2, trans), 4.30 (dd, 2JH-Pt = 59 Hz, 3J = 7.9 Hz, 2J = 0.8 Hz, 1H, =CH2, cis), 2.40 (sbr, 3H, -CH3), 2.31 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.86 (-(C=O)-CH3), 164.89 (Ar-(C=O)), 151.71 (C2), 145.96 (C4), 132.54 (C6), 127.47 (C5), 125.20 (C3), 121.63 (C1), 77.81 (C2′), 65.16 (C1′), 65.14 (C3′), 21.28 (-CH3), 21.25 (-OAc). HR-ESI-MS (m/z): 534.9586 ([M-K]−, calcd for C13H14Cl3O4Pt: 534.9575). CE-purity: 97.1%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-5-methylbenzoate]platinate(II) (5-CH3-ASA-Prop-PtCl3). Bright yellow needles; yield: 87%. 1H NMR (400 MHz, acetone-d6): δ = 7.90 (d, 4J = 2.3 Hz, 1H, Ar-H6), 7.44 (dd, 3J = 8.3 Hz, 4J = 2.3 Hz, 1H, Ar-H4), 7.05 (d, 3J = 8.2 Hz, 1H, Ar-H3), 5.00 (dddd, 2JH-Pt = 59 Hz, 3J = 13.0 Hz, 3J = 7.8 Hz, 3J = 5.4 Hz, 3J = 5.4 Hz, 1H, -CH=), 4.89 (dd, 3JH-Pt = 35 Hz, 2J = 12.0 Hz, 3J = 5.4 Hz, 1H, -OCHαHβ-), 4.49 (dd, 3JH-Pt = 44 Hz, 2J = 12.0 Hz, 3J = 7.8 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 73 Hz, 3J = 12.7 Hz, 2J = 1.3 Hz, 1H, =CH2, trans), 4.30 (dd, 2JH-Pt = 59 Hz, 3J = 7.8 Hz, 2J = 1.3 Hz, 1H, =CH2, cis), 2.39 (sbr, 3H, -CH3), 2.30 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.95 (-(C=O)-CH3), 165.11 (Ar-(C=O)), 149.41 (C2), 136.57 (C5), 135.11 (C4), 132.77 (C6), 124.50 (C3), 124.23 (C1), 77.64 (C2′), 65.30 (C1′), 65.17 (C3′), 21.24 (-OAc), 20.64 (-CH3). HR-ESI-MS (m/z): 534.9587 ([M-K]−, calcd for C13H14Cl3O4Pt: 534.9578). CE-purity: 97.1%.
Potassium trichlorido[η2-(prop-2-en-1-yl)-2-acetoxy-6-methylbenzoate]platinate(II) (6-CH3-ASA-Prop-PtCl3). Bright yellow needles; yield: 73%. 1H NMR (400 MHz, acetone-d6): δ = 7.38 (dd, 3J = 7.9 Hz, 3J = 7.9 Hz, 1H, Ar-H4), 7.23-7.17 (m, 1H, Ar-H5), 7.03 (d, 3J = 8.1 Hz, 1H, Ar-H3), 5.12-4.85 (m, 2JH-Pt = 62 Hz, 3JH-Pt = 34 Hz, 2H, -CH= and -OCHαHβ-), 4.51 (dd, 3JH-Pt = 45 Hz, 2J = 11.5 Hz, 3J = 7.2 Hz, 1H, -OCHαHβ-), 4.34 (dd, 2JH-Pt = 74 Hz, 3J = 11.8 Hz, 2J = 1.4 Hz, 1H, =CH2, trans), 4.30 (dd, 2JH-Pt = 62 Hz, 3J = 7.6 Hz, 2J = 1.6 Hz, 1H, =CH2, cis), 2.44 (sbr, 3H, -CH3), 2.26 (s, 3H, -OAc). 13C NMR (101 MHz, acetone-d6): δ = 169.37 (-(C=O)-CH3), 166.72 (Ar-(C=O)), 149.35 (C2), 138.65 (C6), 131.25 (C4), 128.56 (C5), 127.83 (C1), 121.45 (C3), 77.43 (C2′), 65.45 (C1′), 65.03 (C3′), 21.06 (-OAc), 20.24 (-CH3). HR-ESI-MS (m/z): 534.9587 ([M-K]−, calcd for C13H14Cl3O4Pt: 534.9578). CE-purity: 98.2%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-3-methylbenzoate]platinate(II) (3-CH3-ASA-But-PtCl3). Yellow powder; yield: 82%. 1H NMR (400 MHz, acetone-d6): δ = 7.98–7.80 (m, 1H, Ar-H6), 7.51 (dq, 3J = 7.6 Hz, 4J = 0.8 Hz, 1H, Ar-H4), 7.27 (dd, 3J = 7.7 Hz, 3J = 7.7 Hz, 1H, Ar-H5), 5.15–4.89 (m, 2JH-Pt = 62 Hz, 1H, -CH=), 4.71–4.56 (m, 2H, -OCH2-), 4.35–4.12 (m, 2JH-Pt = 62 Hz, 2H, =CH2), 2.57 (ddt, 2J = 14.1 Hz, 3J = 8.0 Hz, 3J = 6.0 Hz, 1H, -CHαHβ-), 2.33 (s, 3H, -OAc), 2.21 (s, 3H, -CH3), 2.10–2.00 (m, 1H, -CHαHβ-). 13C NMR (101 MHz, acetone-d6): δ = 169.32 (-(C=O)-CH3), 165.31 (Ar-(C=O)), 150.20 (C2), 135.94 (C4), 133.08 (C3), 130.10 (C6), 126.44 (C5), 124.67 (C1), 84.17 (C3′), 65.94 (C4′), 64.80 (C1′), 33.38 (C2′), 20.93 (-OAc), 16.13 (-CH3). HR-ESI-MS (m/z): 547.9763 ([M-K]−, calcd for C14H16Cl3O4Pt: 547.9756). CE-purity: 99.3%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-4-methylbenzoate]platinate(II) (4-CH3-ASA-But-PtCl3). Yellow powder; yield: 28%. 1H NMR (400 MHz, acetone-d6): δ = 7.97 (d, 3J = 8.0 Hz, 1H, Ar-H6), 7.19 (dq, 3J = 8.0 Hz, 4J = 0.8 Hz, 1H, Ar-H5), 6.99 (d, 4J = 0.8 Hz, 1H, Ar-H3), 5.01 (dddd, 2JH-Pt = 64 Hz, 3J = 13.7 Hz, 3J = 7.7 Hz, 3J = 6.3 Hz, 3J = 6.3 Hz, 1H, -CH=), 4.68–4.55 (m, 2H, -OCH2-), 4.35–4.11 (m, 2JH-Pt = 62 Hz, 2H, =CH2), 2.56 (ddt, 2J = 12.2 Hz, 3J = 8.0 Hz, 3J = 6.1 Hz, 1H, -CHαHβ-), 2.39 (s, 3H, -CH3), 2.29 (s, 3H, -OAc), 2.08–1.99 (m, 1H, -CHαHβ-). 13C NMR (101 MHz, acetone-d6): δ = 169.77 (-(C=O)-CH3), 165.02 (Ar-(C=O)), 151.77 (C2), 145.86 (C4), 132.41 (C6), 127.49 (C5), 125.21 (C3), 121.73 (C1), 84.26 (C3′), 65.94 (C4′), 64.63 (C1′), 33.41 (C2′), 22.24 (-CH3), 21.16 (-OAc). HR-ESI-MS (m/z): 547.9778 ([M-K]−, calcd for C14H16Cl3O4Pt: 547.9756). CE-purity: 98.5%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-5-methylbenzoate]platinate(II) (5-CH3-ASA-But-PtCl3). Yellow powder; yield: 97%. 1H NMR (400 MHz, acetone-d6): δ = 7.88 (d, 4J = 2.3 Hz, 1H, Ar-H6), 7.43 (dd, 3J = 8.1 Hz, 4J = 2.2 Hz, 1H, Ar-H4), 7.05 (d, 3J = 8.2 Hz, 1H, Ar-H3), 5.17–4.86 (m, 2JH-Pt = 61 Hz, 1H, -CH=), 4.72–4.53 (m, 2H, -OCH2-), 4.40–4.10 (m, 2JH-Pt = 60 Hz, 2H, =CH2), 2.56 (ddt, 2J = 14.2 Hz, 3J = 8.0 Hz, 3J = 6.0 Hz, 1H, -CHαHβ-), 2.38 (s, 3H, -CH3), 2.28 (s, 3H, -OAc), 2.09–1.98 (m, 1H, -CHαHβ-). 13C NMR (101 MHz, acetone-d6): δ = 169.87 (-(C=O)-CH3), 165.22 (Ar-(C=O)), 149.46 (C2), 136.59 (C5), 135.05 (C4), 132.63 (C6), 124.51 (C3), 124.31 (C1), 84.20 (C3′), 65.94 (C4′), 64.76 (C1′), 33.34 (C2′), 21.13 (-OAc), 20.66 (-CH3). HR-ESI-MS (m/z): 547.9766 ([M-K]−, calcd for C14H16Cl3O4Pt: 547.9756). CE-purity: 99.2%.
Potassium trichlorido[η2-(but-3-en-1-yl)-2-acetoxy-6-methylbenzoate]platinate(II) (6-CH3-ASA-But-PtCl3). Yellow powder; yield: 82%. 1H NMR (400 MHz, acetone-d6): δ = 7.37 (dd, 3J = 7.9 Hz, 3J = 7.9 Hz, 1H, Ar-H4), 7.17 (d, 3J = 7.6 Hz, 1H, Ar-H5), 7.02 (d, 3J = 8.1 Hz, 1H, Ar-H3), 4.98 (dddd, 2JH-Pt = 68 Hz, 3J = 12.2 Hz, 3J = 8.1 Hz, 3J = 6.3 Hz, 3J = 6.3 Hz, 1H, -CH=), 4.68 (dd, 3J = 7.4 Hz, 3J = 6.2 Hz, 2H, -OCH2-), 4.38–4.08 (m, 2JH-Pt = 60 Hz, 2H, =CH2), 2.55 (ddt, 2J = 14.0 Hz, 3J = 8.0 Hz, 3J = 6.0 Hz, 1H, -CHαHβ-), 2.39 (s, 3H, -CH3), 2.26 (s, 3H, -OAc), 2.07–1.97 (m, 1H, -CHαHβ-). 13C NMR (101 MHz, acetone-d6): δ = 169.34 (-(C=O)-CH3), 166.99 (Ar-(C=O)), 149.34 (C2), 138.42 (C6), 131.16 (C4), 128.52 (C5), 128.08 (C1), 121.49 (C3), 83.94 (C3′), 65.98 (C4′), 65.11 (C1′), 33.41 (C2′), 21.05 (-OAc), 20.03 (-CH3). HR-ESI-MS (m/z): 547.9766 ([M-K]−, calcd for C14H16Cl3O4Pt: 547.9756). CE-purity: 100.0%.