3.2. Synthesis
Different β-hydroxydithiocinnamic acid alkyl esters were prepared as described before [
18,
50]. The (PhCN)
2PtCl
2/ (PhCN)
2PdCl
2 as starting materials were prepared using modified literature methods [
69,
70].
General Procedure 1: Metal(II) Complexes with β-Hydroxydithiocinnamic Acid Alkyl esters as Ligands (M1–M6)
The corresponding ligand L1–L6 (2 equiv.), corresponding metal salt (1 equiv.), and sodium acetate (2 equiv.) were dissolved in 15 mL acetonitrile and stirred for 15 h at rt. The precipitated red crystals were filtered, washed with acetonitrile and pentane, and dried under reduced pressure.
[Ni(1-(2-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni1)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L1 (506 mg, 2 mmol) were used. Yield: 240 mg (44.8 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.59 (s, 6H, -SCH3); 3.88 (s, 6H, -OCH3); 6.89–6.97 (m, 4H, -Ar-m-H); 7.28 (s, 2H, =CH); 7.40 (m, 2H, -Ar-p-H); 7.34 (d, 3JH-H=7.4 Hz, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 16.9 (-SCH3); 55.8 (-OCH3); 111.7 (-Ar-m-C); 115.1 (=CH); 120.8 (-Ar-m-C); 127.9 (-Ar-C1); 131.4 (-Ar-m-C); 132.2 (-Ar-o-C); 157.2 (-Ar-C-OCH3); 178.1 (-C-O-); 181.4 (-C=S). Electron ionization mass spectrometry (MS (EI)): m/z = 536 [M(58Ni)]•+. Elemental analysis: calculated for C22H22O4NiS4 C: 49.18 %; H: 4.13 %, found: C: 49.36 %; H: 4.14 %.
[Ni(1-(3-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni2)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L2 (506 mg, 2 mmol) were used. Yield: 300 mg (56.0 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.65 (s, 6H, -SCH3); 3.86 (s, 6H, -OCH3); 7.10 (d, 3JH-H=8.8 Hz, 2H, -Ar-o-H); 7.16 (s, 2H, =CH); 7.40 (m, 2H, -Ar-p-H); 7.34 (m, 2H, -Ar-m-H); 7.47 (m, 2H, -Ar-p-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 16.9 (-SCH3); 55.8 (-OCH3); 111.7 (-Ar-m-C); 115.1 (=CH); 120.8 (-Ar-m-C); 127.9 (-Ar-C1); 131.4 (-Ar-m-C); 132.2 (-Ar-o-C); 157.2 (-Ar-C-OCH3); 178.1 (-C-O-); 181.4 (-C=S). MS (EI): m/z = 536 [M(58Ni)]•+. Elemental analysis: calculated for C22H22O4NiS4 C: 49.18 %; H: 4.13 %, found: C: 49.45 %; H: 4.15 %.
[Ni(1-(4-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni3)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L3 (506 mg, 2 mmol) were used. Yield: 350 mg (65.3 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.63 (s, 6H, -SCH3); 3.89 (s, 6H, -OCH3); 6.92 (d, 3JH-H=8.8 Hz, 4H, -Ar-o-H); 7.10 (s, 2H, =CH); 7.88 (d, 3JH-H=8.9 Hz, 4H, -Ar-m-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 16.6 (-SCH3); 55.5 (-OCH3); 110.0 (=CH); 113.8 (-Ar-o-C); 129.4 (-Ar-m-C); 130.3 (-Ar-C1); 162.5 (-Ar-C-OCH3); 177.8 (-C-O-); 181.6 (-C=S). MS (EI): m/z = 536 [M(58Ni)]•+. Elemental analysis: calculated for C22H22O4NiS4 C: 49.18 %; H: 4.13 %, found: C: 49.26 %; H: 4.10 %.
[Ni(1-(2-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni4)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L4 (540 mg, 2 mmol) were used. Yield: 250 mg (44.3 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.48 (m, 6H, -OCH2CH3); 2.61 (t, 6H, -CH3); 4.11 (q, 3JH-H=6.9 Hz, 4H, -OCH2CH3); 6.90-6.96 (m, 4H, -Ar-m-H); 7.28-7.46 (m, 2H, -Ar-p-H); 7.79-7.81 (m, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.9 (-OCH2CH3); 16.7 (-CH3); 64.5 (-OCH2CH3); 112.8 (-Ar-m-C); 115.0 (=CH); 120.7 (-Ar-m-C); 127.8 (=C-OH); 131.6 (-Ar-o-C); 132.3 (-Ar-p-C); 156.7 (qC, -Ar-o-C); 177.9 (Ar-C1); 181.1 (-C=S). MS (EI): m/z = 564 [M(58Ni)]•+. Elemental analysis: calculated for C24H26O4NiS4 C: 50.98 %; H: 4.64 %, found: C: 50.99 %; H: 4.63 %.
[Ni(1-(3-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni5)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L5 (540 mg, 2 mmol) were used. Yield: 200 mg (35.5 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.57 (m, 6H, -OCH2CH3); 2.66 (t, 6H, -CH3); 4.07 (q, 3JH-H=7.1 Hz, 4H, -OCH2CH3); 7.08 (d, 2H, 3JH-H=8.0 Hz, -Ar-p-H); 7.15 (s, 2H, =CH); 7.33 (m, 2H, -Ar-m-H); 7.41 (s, 2H, -Ar-o-H); 7.47 (d, 2H, 3JH-H=7.8 Hz, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.7 (-OCH2CH3); 17.1 (-CH3); 63.7 (-OCH2CH3); 108.0 (=CH); 112.4 (-Ar-o-C); 118.3 (-Ar-p-C); 118.9 (-Ar-o-C); 129.7 (-Ar-m-C); 159.2 (qC, -Ar-m-C); 169.1 (Ar-C1); 217.2 (-C=S). MS (EI): m/z = 564 [M(58Ni)]•+. Elemental analysis: calculated for C24H26O4NiS4 C: 50.98 %; H: 4.64 %, found: C: 51.08 %; H: 4.63 %.
[Ni(1-(4-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Ni6)
Synthesis was performed according to general procedure 1. NiCl2·6H2O (250 mg, 1 mmol) and L6 (540 mg, 2 mmol) were used. Yield: 190 mg (33.7 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.37 (t, 3JH-H=6.9 Hz, 6H, -OCH2CH3); 2.53 (s, 6H, -CH3); 4.02 (q, 3JH-H=6.9 Hz, 4H, -OCH2CH3); 6.81 (d, 4H, 3JH-H=8.6 Hz, -Ar-m-H); 7.01 (s, 2H, =CH); 7.78 (d, 4H, 3JH-H=8.6 Hz, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.7 (-OCH2CH3); 16.6 (-CH3); 63.7 (-OCH2CH3); 110.0 (=CH); 114.2 (-Ar-m-C); 130.1 (-Ar-C1); 162.0 (-Ar-C-OCH3); 177.8 (-C-O-); 181.5 (-C=S). MS (EI): m/z = 564 [M(58Ni)]•+. Elemental analysis: calculated for C24H26O4NiS4 C: 50.98 %; H: 4.64 %, found: C: 50.91 %; H: 4.60 %.
[Pd(1-(2-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd1)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (399 mg, 1 mmol) and L1 (500 mg, 2 mmol) were used. Yield: 120 mg (20.5 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.66 (s, 6H, -SCH3); 3.90 (s, 6H, -OCH3); 6.93-7.01 (m, 4H, -Ar-m-H/-Ar-o-H); 7.19 (s, 2H, =CH); 7.42 (m, 2H, -Ar-p-H); 7.79 (d, 3JH-H=7.6 Hz, 4JH-H=1.8 Hz, 2H, -Ar-m-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.5 (-SCH3); 55.9 (-OCH3); 111.8 (-Ar-m-C); 115.3 (=CH); 120.7 (-Ar-m-C); 129.0 (-Ar-C1); 130.4 (-Ar-m-C); 131.2 (-Ar-o-C); 157.4 (-Ar-C-OCH3); 179.2 (-C-O-); 180.2 (-C=S). MS (EI): m/z = 564 [M(106Pd)]•+. Elemental analysis: calculated for C22H22O4PdS4 C: 45.16 %; H: 3.79 %, found: C: 45.23 %; H: 3.72 %.
[Pd(1-(3-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd2)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (399 mg, 1 mmol) and L2 (500 mg, 2 mmol) were used. Yield: 150 mg (25.7 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.71 (s, 6H, -SCH3); 4.09 (s, 6H, -OCH3); 7.09 (dd, 3JH-H=8.1 Hz, 4JH-H=2.4 Hz, 2H, -Ar-o-H); 7.16 (s, 2H, =CH); 7.34 (m, 2H, -Ar-m-H); 7.54-7.57 (m, 2H, -Ar-p-H); 7.65 (m, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.5 (-SCH3); 55.4 (-OCH3); 110.8 (-Ar-m-C); 113.0 (=CH); 117.9 (-Ar-m-C); 120.0 (-Ar-C1); 129.4 (-Ar-m-C); 139.7 (-Ar-o-C); 159.8 (-Ar-C-OCH3); 178.1 (-C-O-). MS (EI): m/z = 564 [M(106Pd)]•+. Elemental analysis: calculated for C22H22O4PdS4 C: 45.16 %; H: 3.79 %, found: C: 45.40 %; H: 3.75 %.
[Pd(1-(4-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd3)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (399 mg, 1 mmol) and L3 (500 mg, 2 mmol) were used. Yield: 60 mg (10.3 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.70 (s, 6H, -SCH3); 3.91 (s, 6H, -OCH3); 6.97 (d, 3JH-H=8.7 Hz, 4H, -Ar-o-H); 7.13 (s, 2H, =CH); 8.02 (d, 3JH-H=9.1 Hz, 4H, -Ar-m-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.4 (-SCH3); 55.5 (-OCH3); 110.5 (=CH); 113.9 (-Ar-o-C); 130.0 (-Ar-m-C); 130.3 (-Ar-C1); 162.7 (-Ar-C-OCH3); 178.1 (-C-O-); 180.4 (-C=S). MS (EI): m/z = 564 [M(106Pd)]•+. Elemental analysis: calculated for C22H22O4PdS4 C: 45.16 %; H: 3.79 %, found: C: 45.23 %; H: 3.80 %.
[Pd(1-(2-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd4)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (600 mg, 1.5 mmol) and L4 (700 mg, 2.9 mmol) were used. Yield: 80 mg (13.1 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.28 (m, 6H, -OCH2CH3); 2.66 (s, 6H, -CH3); 4.17 (q, 3JH-H=7.0 Hz, 4H, -OCH2CH3); 6.95-7.02 (m, 4H, -Ar-m-H); 7.44-7.61 (m, 4H, -Ar-p-H/=CH); 7.75-7.84 (m, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.9 (-OCH2CH3); 16.7 (-CH3); 64.5 (-OCH2CH3); 112.8 (-Ar-m-C); 115.0 (=CH); 120.7 (-Ar-m-C); 127.8 (=C-OH); 131.6 (-Ar-o-C); 132.3 (-Ar-p-C); 156.7 (qC, -Ar-o-C); 177.9 (Ar-C1); 181.1 (-C=S). No EI mass spectrum could be obtained. Elemental analysis: calculated for C24H26O4PdS4 C: 47.02 %; H: 4.26 %, found: C: 47.41 %; H: 4.26 %.
[Pd(1-(3-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd5)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (399 mg, 1 mmol) and L5 (500 mg, 2.1 mmol) were used. Yield: 120 mg (16.6 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.46 (t, 3JH-H=7.0 Hz, 6H, -OCH2CH3); 2.71 (s, 6H, -CH3); 4.13 (q, 3JH-H=7.0 Hz, 4H, -OCH2CH3); 7.07-7.09 (m, 2H, -Ar-p-H); 7.13 (s, 2H, =CH); 7.32 (m, 2H, -Ar-m-H); 7.54-7.58 (m, 4H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.8 (-OCH2CH3); 17.5 (-CH3); 63.6 (-OCH2CH3); 110.9 (=CH); 113.5 (-Ar-o-C); 118.5 (-Ar-p-C); 120.0 (-Ar-o-C); 129.4 (-Ar-m-C); 159.1 (qC, -Ar-m-C); 178.4 (Ar-C1); 182.6 (-C=S). MS (EI): m/z = 612 [M(106Pd)]•+. Elemental analysis: calculated for C24H26O4PdS4 C: 47.02 %; H: 4.27 %, found: C: 46.68 %; H: 4.24 %.
[Pd(1-(4-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pd6)
Synthesis was performed according to general procedure 1. (PhCN)2PdCl2 (399 mg, 1 mmol) and L6 (500 mg, 2.1 mmol) were used. Yield: 100 mg (16.3 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.47 (t, 3JH-H=6.9 Hz, 6H, -OCH2CH3); 2.70 (s, 6H, -CH3); 4.14 (q, 3JH-H=6.9 Hz, 4H, -OCH2CH3); 6.95 (d, 4H, 3JH-H=8.8 Hz, -Ar-m-H); 7.13 (s, 2H, =CH); 8.00 (d, 4H, 3JH-H=8.9 Hz, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.7 (-OCH2CH3); 17.4 (-CH3); 63.7 (-OCH2CH3); 110.0 (=CH); 114.3 (-Ar-m-C); 130.0 (-Ar-C1). MS (EI): m/z = 612 [M(106Pd)]•+. Elemental analysis: calculated for C24H26O4PdS4 C: 47.02 %; H: 4.27 %, found: C: 47.35 %; H: 4.32 %.
[Pt(1-(2-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pt1)
Synthesis was performed according to general procedure 1. (PhCN)2PtCl2 (492 mg, 1 mmol) and L1 (500 mg, 1 mmol) were used. Yield: 60 mg (8.9 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.63 (s, 6H, -SCH3); 3.89 (s, 6H, -OCH3); 6.92-7.11 (m, 4H, -Ar-m-H/-Ar-o-H); 7.20 (s, 2H, =CH); 7.43-7.54 (m, 2H, -Ar-p-H); 7.82 (dd, 3JH-H=7.6 Hz, 4JH-H=1.7 Hz, 2H, -Ar-m-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.5 (-SCH3); 55.8 (-OCH3); 111.9 (-Ar-m-C); 117.1 (=CH); 120.4 (-Ar-m-C); 129.1 (-Ar-C1); 130.4 (-Ar-m-C); 131.9 (-Ar-o-C). MS (EI): m/z = 673 [M(195Pt)]•+. Elemental analysis: calculated for C22H22O4PtS4 C: 39.22 %; H: 3.29 %, found: C: 39.36 %; H: 3.32 %.
[Pt(1-(3-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pt2)
Synthesis was performed according to general procedure 1. (PhCN)2PtCl2 (470 mg, 1 mmol) and L2 (506 mg, 1 mmol) were used. Yield: 290 mg (43.1 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.66 (s, 6H, -SCH3); 3.91 (s, 6H, -OCH3); 7.12 (dd, 3JH-H=8.4 Hz, 4JH-H=2.5 Hz, 2H, -Ar-o-H); 7.14 (s, 2H, =CH); 7.32 (m, 2H, -Ar-m-H); 7.59 (d, 3JH-H=7.8 Hz, 2H, -Ar-p-H); 7.67 (m, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.6 (-SCH3); 55.4 (-OCH3); 112.5 (-Ar-m-C); 112.5 (=CH); 117.5 (-Ar-m-C); 119.4 (-Ar-C1); 129.6 (-Ar-m-C); 140.3 (-Ar-o-C); 160.0 (-Ar-C-OCH3). MS (EI): m/z = 673 [M(195Pt)]•+. Elemental analysis: calculated for C22H22O4PtS4 C: 39.22 %; H: 3.29 %, found: C: 39.11 %; H: 3.25 %.
[Pt(1-(4-methoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pt3)
Synthesis was performed according to general procedure 1. (PhCN)2PtCl2 (470 mg, 1 mmol) and L3 (506 mg, 1 mmol) were used. Yield: 210 mg (31.2 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 2.72 (s, 6H, -SCH3); 3.90 (s, 6H, -OCH3); 7.00 (d, 3JH-H=9.0 Hz, 4H, -Ar-o-H); 7.02 (s, 2H, =CH); 8.04 (d, 3JH-H=8.9 Hz, 4H, -Ar-m-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 17.5 (-SCH3); 55.5 (-OCH3); 112.0 (=CH); 114.1 (-Ar-o-C); 129.3 (-Ar-m-C); 131.4 (-Ar-C1); 162.3 (-Ar-C-OCH3); 173.6 (-C-O-). MS (EI): m/z = 673 [M(195Pt)]•+. Elemental analysis: calculated for C22H22O4PtS4 C: 39.22 %; H: 3.29 %, found: C: 39.29 %; H: 3.32 %.
[Pt(1-(2-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pt4)
Synthesis was performed according to general procedure 1. (PhCN)2PtCl2 (700 mg, 1.5 mmol) and L4 (700 mg, 2.9 mmol) were used. Yield: 120 mg (17.1 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.28 (m, 3JH-H=7.2 Hz, 6H, -OCH2CH3); 2.66 (s, 6H, -CH3); 4.17 (q, 3JH-H=7.2 Hz, 4H, -OCH2CH3); 6.95-7.02 (m, 4H, -Ar-m-H); 7.44-7.50 (m, 4H, -Ar-p-H/=CH); 7.75-7.83 (m, 2H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.9 (-OCH2CH3); 16.7 (-CH3); 64.5 (-OCH2CH3); 112.3 (-Ar-m-C); 115.0 (=CH); 120.7 (-Ar-m-C); 127.8 (=C-OH); 131.6 (-Ar-o-C); 132.3 (-Ar-p-C); 156.7 (qC, -Ar-o-C); 177.9 (Ar-C1); 181.1 (-C=S). No EI mass spectrum could be obtained. Elemental analysis: calculated for C24H26O4PtS4 C: 41.08 %; H: 3.73 %, found: C: 41.18 %; H: 3.25 %.
[Pt(1-(3-ethoxyphenyl)-3-(methylthio)-3-thioxo-prop-1-en-1-olate-O,S)] (Pt5)
Synthesis was performed according to general procedure 1. (PhCN)2PtCl2 (470 mg, 1 mmol) and L5 (510 mg, 2 mmol) were used. Yield: 210 mg (30.0 %) as red crystals. 1H NMR (400 MHz, CDCl3): δ = 1.45 (t, 3JH-H=7.1 Hz, 6H, -OCH2CH3); 2.65 (s, 6H, -CH3); 4.13 (q, 3JH-H=6.9 Hz, 4H, -OCH2CH3); 7.09-7.13 (m, 4H, -Ar-p-H/ =CH); 7.31 (m, 2H, -Ar-m-H); 7.58-7.60 (m, 4H, -Ar-o-H). 13C{1H} NMR (101 MHz, CDCl3): δ = 14.8 (-OCH2CH3); 17.6 (-CH3); 63.6 (-OCH2CH3); 112.5 (=CH); 112.9 (-Ar-o-C); 118.0 (-Ar-p-C); 119.4 (-Ar-o-C); 129.5 (-Ar-m-C); 159.3 (qC, -Ar-m-C); 177.8 (Ar-C1). MS (EI): m/z = 701 [M(195Pt)]•+. Elemental analysis: calculated for C24H26O4PtS4 C: 41.08 %; H: 3.73 %, found: C: 41.03 %; H: 3.78 %.