Supporting information for: [https://doi.org/10.1021/acs.organomet.5b00041]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1746

Aranđelović, Sandra

Dojčinović, Biljana P.

Filipović, Vuk

Grgurić-Šipka, Sanja

Nikolić, Stefan

Opsenica, Dejan M.

Radulović, Siniša

Organometallics

稲飯, 幸代

Tokushima University Institutional Repository

キンセイ ジョウシ ユライ ノ トシ コウエン ニオケル シゼン リョクチ ノ セイタイテキ・シャカイテキ ヒョウカ

Faculty of Chemistry Repository - Cherry

               Supplementary data for article:           Nikolić, S.; Opsenica, D. M.; Filipović, V.; Dojčinović, B.; Arandelović, S.; Radulović, S.; Grgurić-Šipka, S. Strong in Vitro Cytotoxic Potential of New Ruthenium-Cymene Complexes. Organometallics 2015, 34 (14), 3464–3473. https://doi.org/10.1021/acs.organomet.5b00041   S1  Supporting Information  Strong in vitro Cytotoxic Potential of New Ruthenium-Cymene Complexes  Stefan Nikolić†, Dejan M. Opsenica‡*, Vuk Filipović‡, Biljana Dojčinović‡, Sandra Aranđelović§, Siniša Radulović§, Sanja Grgurić-Šipka†*  †Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade, Serbia ‡Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11 000, Belgrade, Serbia §Institute for Oncology and Radiology of Serbia, Pasterova 14, 11000 Belgrade, Serbia   Table of contents  Mass spectra………………………………………………………….….S2 NMR spectra………………………………………………………….….S4–S23 MTT bioassay graphics………………………………………………….S24    S2  Figure S1: (+)ESI-MS (m/z) C1 [(η6-p-cymene)Ru(L1-H)]+ calculated 472.01776, found 472.0189, in MeOH + 0.1% TFA.        OB1733 #1-127 RT: 0.01-1.00 AV: 127 NL: 6.71E7T: FTMS + c ESI Full ms [200.00-800.00]200 250 300 350 400 450 500 550 600 650 700 750 800m/z05101520253035404550556065707580859095100Relative Abundance472.0189z=1220.9933z=1252.0322z=1282.2794z=?675.0439z=1385.4940z=2479.5409z=?535.9817z=1413.0355z=1352.3134z=? 647.4594z=1709.0321z=1770.9786z=1503.9903z=?463.3043z=?581.9873z=?OB1733 #1-127 RT: 0.01-1.00 AV: 127 NL: 6.71E7T: FTMS + c ESI Full ms [200.00-800.00]430 435 440 445 450 455 460 465 470 475 480 485 490 495 500 505 510 515 520m/z05101520253035404550556065707580859095100Relative Abundance472.0189z=1474.0181z=1470.0199z=1476.0161z=1466.0229z=1479.5409z=? 495.4157z=?503.9903z=?439.3537z=?429.9967z=?463.3043z=?455.0578z=?516.0448z=?445.0077z=?508.3331z=?491.0170z=?S3  Figure S2: (+)ESI-MS (m/z) C2[(η6-p-cymene)Ru(L2-H)]+ Calculated 382.084664, found 382.0903, in MeOH + 0.1% TFA.          S4  Figure S3: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L1 C1_1H NMR.esp9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)1.455.450.652.510.401.070.253.440.221.120.920.501.650.490.99DMSO8.8908.8798.5928.3558.3378.1698.0998.0957.7677.7627.7487.7445.8225.8095.7795.7665.5565.5443.3663.1672.8592.8452.8312.8172.8032.1062.0862.0181.7961.1981.1841.1341.1261.1201.112L1_1H NMR.esp8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6Chemical Shift (ppm)2.011.011.011.200.971.008.8358.8268.3338.2828.1188.1008.0528.0488.0188.0087.6877.6847.6697.666NNHClSNH2L12344a56788awater  S5  Figure S4: 13C{1H} NMR (125 MHz, DMSO-d6)spectrum of ligand L1 L1_13C NMR.esp230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10Chemical Shift (ppm)39.01139.17739.34339.50939.67539.84140.015115.685121.591124.739126.652127.793134.191143.238149.130151.787182.206L1_13C NMR.esp150 148 146 144 142 140 138 136 134 132 130 128 126 124 122 120 118 116Chemical Shift (ppm)115.685121.591124.739126.652127.793134.191143.238149.130151.787NNHClSNH2L12344a56788a S6  Figure S5: 1H NMR (200 MHz, DMSO-d6) spectrum of complex C1 C1_1H NMR.esp12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0Chemical Shift (ppm)1.455.450.652.510.401.070.253.440.221.120.920.501.650.490.99DMSO1.1121.1201.1261.1341.1841.1981.7962.0182.0862.1062.8032.8172.8312.8452.8593.1673.3665.5445.5565.7665.7795.8095.8227.7447.7487.7627.7678.0998.3378.3558.5928.8798.890C1_1H NMR.esp8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6Chemical Shift (ppm)0.221.120.920.501.650.490.997.7447.7487.7627.7678.0958.0998.1658.1698.3378.3558.5928.8798.890waterNNHClSNH2RuClC1Cl-2344a56788a91011 121314 1516'1611' 12'  S7  Figure S6: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand C1 C1_13C NMR.esp230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10Chemical Shift (ppm)17.69117.84218.44921.47422.17423.96529.94430.81739.01239.17939.34539.51139.67739.84340.00979.02880.70385.48386.335100.061100.610106.350113.311120.502125.210127.196128.777135.557145.961149.377182.027C1_13C NMR.esp145 140 135 130 125 120 115 110 105 100Chemical Shift (ppm)100.061100.610106.350113.311120.502125.210126.055127.196128.777135.557145.961149.377NNHClSNH2RuClC1Cl-2344a56788a91011 121314 1516'1611' 12'    S8  Figure S7: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L1 δH 9.22 (1H, br s, S=C-NH), 9.07 (1H, d, 3J(H2, H3) = 6.7 Hz, H2), 9.05 (1H, br s, S=C-NH), 8.99 (1H, d, 3J(H2, H3) = 6.7 Hz, H3), 8.81 (1H, d, 3J(H5, H6) = 9.2 Hz, H5), 8.22 (1H, d, 4J(H6, H8) = 2.1 Hz, H8), 7.91 (1H, dd, 3J(H5, H6) = 9.2 Hz, 4J(H6, H8)  = 2.1 Hz, H6). L1_1H NMR_NH hsqc.esp10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)1.000.970.971.051.900.90DMSOWater9.2159.0769.0638.9998.9858.8168.7978.2197.9207.9167.902L1_1H NMR_NH hsqc.esp9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9Chemical Shift (ppm)1.000.970.971.051.900.909.2159.0769.0639.0468.9998.9858.8168.7978.2198.2157.9207.9167.902NNHClSNH2L12344a56788a S9  Figure S8: 1H-15N HSQCNMR (500 MHz, DMSO-d6) spectrum of ligand L1 L1_15N.999.001.2rr.esp9.5 9.0 8.5 8.0F2 Chemical Shift (ppm)-250-200-150-100-50050100150200250300350400450500550600650F1 Chemical Shift (ppm)15N 131.02 ppm9.22 ppm9.05 ppmNNHClSNH2L12344a56788a   S10  Figure S9: 1H NMR (500 MHz, DMSO-d6) spectrum of complex C1 δH 8.90 (1H, d, 3J(H2, H3) = 5.5 Hz, H2), 8.67 (1H, bs S=C-NH), 8.57-8.47 (3H, m, H3, H5 and S=C-NH), 8.12 (1H, d, 4J(H6, H8) = 2.1 Hz, H8), 7.76 (1H, dd, 3J(H5, H6) = 9.0 Hz, 4J(H6, H8) = 2.3 Hz, H6), 5.73 - 5.84 (4H, m, H11, H11'', H12 and H12'), 2.88-2.76 (1H, m, H15), 2.08 (3H, s, H14), 1.19 (6H, d, 3J(H15, H16) = 7.02 Hz, H16 and H16'). C1_1H NMR_NH hsqc.esp9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)3.867.101.243.251.564.551.361.002.921.181.44M03(d)M04(dd)M06(d)M01(d)M07(dt)M05(m)M02(m)1.1081.1221.1801.1942.0212.0832.1042.2422.5402.5542.8002.8142.8272.8412.8553.1645.5585.5705.7645.7775.8055.8187.7457.7507.7637.7677.7747.7788.1228.1268.2388.5018.5128.5208.6728.8908.901C1_1H NMR_NH hsqc.esp8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8Chemical Shift (ppm)1.361.002.911.181.448.9018.8908.6728.5208.5018.2388.2338.1268.1227.7787.7747.7677.7637.7507.745DMSONNHClSNH2RuClC1Cl-2344a56788a91011 121314 1516'1611' 12'   S11  Figure S10: 1H-15N HSQC NMR (500 MHz, DMSO-d6) spectrum of complex C1 (selected part of spectrum) C1_N-hsqc NMR.esp9.0 8.5 8.0 7.5F2 Chemical Shift (ppm)-250-200-150-100-50050100150200250300350400F1 Chemical Shift (ppm)15N 122.24 ppm8.67 ppm8.57-8.47 ppmNNHClSNH2RuClC1Cl-2344a56788a91011 121314 1516'1611' 12' S12  Figure S11: 1H NMR (200 MHz,DMSO-d6) spectrum of ligand L2xHCl L2xHCl_1H NMR.esp12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)4.134.380.961.000.980.952.003.9554.0116.1657.7777.8027.8197.8418.7068.7158.7238.7578.7658.9428.9659.39211.461L2xHCl_1H NMR.esp9.5 9.0 8.5 8.0Chemical Shift (ppm)0.961.000.980.957.7777.8027.8197.8418.7068.7158.7238.7468.7578.7658.9428.9659.392NNNH x HClL2xHCl23456789DMSO  S13  Figure S12: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand L2xHCl L2xHCl_13C NMR.esp240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40Chemical Shift (ppm)162.885153.308148.393138.470124.906119.86344.68640.97240.53540.13539.71639.29738.87838.460L2xHCl_13C NMR.esp160 155 150 145 140 135 130 125 120 115Chemical Shift (ppm)162.885153.308148.393138.470124.906119.863NNNH x HClL2xHCl23456789 S14  Figure S13: 1H NMR (200 MHz, DMSO-d6) spectrum of complex C2 C2_1H NMR.esp11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)6.983.201.924.064.204.538.658.671.081.190.821.002.27Water10.7059.0969.0858.9198.9148.8978.8888.3158.3078.2968.2768.2688.2568.2427.7127.6867.6707.6477.2017.0246.9626.9286.8896.7856.7515.8195.7855.7775.7434.1234.0644.0273.9293.4913.2972.9042.8702.8342.8002.2102.1152.0161.3281.2891.2331.1991.1351.101C2_1H NMR.esp9.0 8.5 8.0 7.5 7.0Chemical Shift (ppm)4.538.658.671.081.190.821.009.0969.0858.9198.9148.8978.8888.3158.3078.2968.2768.2688.2568.2427.7127.6867.6707.6477.2017.0246.9626.9286.8896.8216.7856.751NClRuClNH+NHC2BPh4-1011 121314 1516'1611' 12'23456789DMSO S15  Figure S14: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand C2 C2_13C NMR.esp168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)18.06821.69130.17638.46038.87839.29739.71640.13540.55340.95444.79685.74386.599100.327106.608119.262121.774124.378125.470125.579125.634135.794136.413149.194155.038162.139163.122163.905164.105165.088C2_13C NMR.esp165 160 155 150 145 140 135 130 125 120Chemical Shift (ppm)119.262121.774124.378125.470125.525125.579125.634135.757135.794136.413149.194155.038162.139163.122163.905164.105165.088NClRuClNH+NHC2BPh4-1011 121314 1516'1611' 12'23456789 S16  Figure S15: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L2 (as base) δH 9.29 (1H, d, 3J(H2, H4) = 1.7 Hz, H2), 8.77 (1H, d, 3J(H5, H6) = 4.5 Hz, 4J(H4, H6) = 1.5 Hz, H6), 8.57 (1H, dt, 3J(H4, H5) = 8.2 Hz, 3J(H2, H4) = 1.8 Hz, H4), 7.58 (1H, ddd, 3J(H4, H5) = 8.1 Hz, 3J(H5, H6) = 4.9 Hz, J = 0.7 Hz, H5), 3.85 (4H, s, H8 and H9). L2_1H NMR_NH hmbc.esp10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)0.580.130.393.980.981.000.971.009.2918.7798.7768.7698.5788.5758.5588.5547.5937.5837.5827.5777.5677.5663.8523.4083.3943.3803.3663.0762.5032.5001.0151.0010.987L2NNNH23456789DMSO Et3NEt3NL2_1H NMR_NH hmbc.esp9.0 8.5 8.0 7.5Chemical Shift (ppm)0.981.000.971.009.2949.2918.7798.7768.7698.7668.5788.5758.5718.5628.5588.5547.5937.5917.5837.5827.5777.575   S17  Figure S16: 1H-15N HMBC NMR (500 MHz, DMSO-d6) spectrum of ligand L2 L2_N-hmbc NMR.esp9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0F2 Chemical Shift (ppm)050100150200250300350400450500F1 Chemical Shift (ppm)15N 316.7 ppm9.29 ppm8.77 ppm3.85 ppm15N 251.0 ppm15N 127.73 ppmL2NNNH23456789  S18  Figure S17: 1H NMR (500 MHz, DMSO-d6) spectrum of complex C2:  δH 9.08 (1H, d, 3J(H2, H4) = 1.9 Hz, H2), 8.90 (1H, dd, 3J(H5, H6) = 4.8 Hz, 3J(H4, H6) = 1.5 Hz, H6), 8.29 (1H, dt, 3J(H4, H5) = 8.0 Hz, 3J(H2, H4)  = 2.0 Hz, H4), 7.70 (1H, ddd, 3J(H4, H5) = 8.8 Hz, 3J(H5, H6) = 4.8 Hz, J = 0.7 Hz, H5), 7.21-7.15 (8H, m, H2-BPh4), 6.92 (8H, t, 3J(H2ʼ, H3ʼ, H4ʼ) = 7.4 Hz, H3-BPh4), 6.82-6.76 (4H, m, H4-BPh4), 5.84-5.75 (4H, m, H11, H11'', H12 and H12'), 4.0 (4H, s, H8 and H9), 2.88-2.78 (1H, m, H15), 2.09 (3H, s, H14), 1.19 (6H, d, 3J(H15, H16) = 7.0 Hz, H16 and H16'). NClRuClNH+NHC2BPh4-1011 121314 1516'1611' 12'23456789C2_1H NMR_NH hmbc.esp9.0 8.5 8.0 7.5 7.0Chemical Shift (ppm)1.232.452.400.270.270.250.266.7746.7886.8036.9086.9236.9387.1677.1707.1777.1807.1857.1887.1907.1937.6847.6927.6947.6997.7007.7087.7108.2778.2818.2858.2938.2978.3018.8938.8968.9028.9069.0819.084C2_1H NMR_NH hmbc.esp10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)1.650.810.340.301.071.161.232.452.400.270.270.250.26DMSOWater1.1551.1871.2011.2351.2492.0872.8062.8202.8342.8473.0503.0653.0793.0943.1723.9323.9975.7635.7765.8085.8216.7746.7886.9086.9236.9387.1707.1777.1857.1907.1967.6847.6927.6947.6997.7087.7108.2778.2818.2858.2938.2978.3018.8968.9028.9069.0819.084Et3NEt3N S19   Figure S18: 1H-15N HMBC NMR (500 MHz, DMSO-d6) spectrum of complex C2 (selected part of spectrum) C2_N-hmbc NMR.esp9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0F2 Chemical Shift (ppm)050100150200250300350400450500F1 Chemical Shift (ppm)9.08 ppm8.90 ppm4.0 ppm15N 317.65 ppm15N 115.33 ppmNClRuClNH+NHC2BPh4-1011 121314 1516'1611' 12'23456789 S20  Figure S19. Stability of complex C1 in 24h period; 1H NMR spectra were recorded in DMSO-d6: a) ligand region; b) p-cymene region.  a)   b)          S21  Figure S20. Stability of complex C2 in 24 h period; 1H NMR spectra were recorded in DMSO-d6:  a) ligand region; b) p-cymene region.  a)  b)        S22  Figure S21. Comparison of 1H NMR spectrum of complex C1 after 24 h period and 1H NMR spectrum of free ligand L1. Spectra were recorded in DMSO-d6.  Figure S22. Comparison of 1H NMR spectrum of complex C2 after 24 h period and 1H NMR spectrum of free ligand L2. Spectra were recorded in DMSO-d6.   S23  Figure S23. Comparison of 1H NMR spectrum of complex C1 after 24 h period and 1H NMR spectrum of complex [Ru(cymene)Cl2DMSO]. Spectra were recorded in DMSO-d6.    Figure S24. Comparison of 1H NMR spectrum of complex C2 after 24 h period and 1H NMR spectrum of complex [Ru(cymene)Cl2DMSO]. Spectra were recorded in dmso-d6.  S24  Figure S25: Cell survival after 72h treatment of A549 cell line with ligands L1, L2, complexes C1, C2 and CDDP.  Figure S26:Cell survival after 72h treatment of HeLa cell line with ligands L1, L2, complexes C1, C2 and CDDP   Figure S27: Cell survival after 72h treatment of MDA-MB-231 cell line with ligands L1, L2, complexes C1, C2 and CDDP   

Supplementary data for article: Nikolić, S.; Opsenica, D. M.; Filipović, V.; Dojčinović, B.; Arandelović, S.; Radulović, S.; Grgurić-Šipka, S. Strong in Vitro Cytotoxic Potential of New Ruthenium-Cymene Complexes. Organometallics 2015, 34 (14), 3464–3473. https://doi.org/10.1021/acs.organomet.5b00041

Cherry - Repository of the Faculty of Chemistry;  University of Belgrade

  
 
 
 
 
 
 
 
 
 
 
 
 
 
Supplementary data for article: 
 
         Nikolić, S.; Opsenica, D. M.; Filipović, V.; Dojčinović, B.; Arandelović, S.; Radulović, S.; 
Grgurić-Šipka, S. Strong in Vitro Cytotoxic Potential of New Ruthenium-Cymene 
Complexes. Organometallics 2015, 34 (14), 3464–3473. 
https://doi.org/10.1021/acs.organomet.5b00041 
 
 
S1 
 
Supporting Information 
 
Strong in vitro Cytotoxic Potential of New Ruthenium-Cymene Complexes  
Stefan Nikolić†, Dejan M. Opsenica‡*, Vuk Filipović‡, Biljana Dojčinović‡, Sandra Aranđelović§, Siniša 
Radulović§, Sanja Grgurić-Šipka†* 
 
†Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade, Serbia 
‡Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11 000, 
Belgrade, Serbia 
§Institute for Oncology and Radiology of Serbia, Pasterova 14, 11000 Belgrade, Serbia 
 
 
Table of contents 
 
Mass spectra………………………………………………………….….S2 
NMR spectra………………………………………………………….….S4–S23 
MTT bioassay graphics………………………………………………….S24 
 
  
S2 
 
Figure S1: (+)ESI-MS (m/z) C1 [(η6-p-cymene)Ru(L1-H)]+ calculated 472.01776, found 472.0189, 
in MeOH + 0.1% TFA. 
 
 
 
 
 
 
 
OB1733 #1-127 RT: 0.01-1.00 AV: 127 NL: 6.71E7
T: FTMS + c ESI Full ms [200.00-800.00]
200 250 300 350 400 450 500 550 600 650 700 750 800
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
R
el
at
iv
e 
A
bu
nd
an
ce
472.0189
z=1
220.9933
z=1
252.0322
z=1
282.2794
z=?
675.0439
z=1
385.4940
z=2
479.5409
z=?
535.9817
z=1413.0355z=1
352.3134
z=? 647.4594z=1
709.0321
z=1
770.9786
z=1
503.9903
z=?
463.3043
z=?
581.9873
z=?
OB1733 #1-127 RT: 0.01-1.00 AV: 127 NL: 6.71E7
T: FTMS + c ESI Full ms [200.00-800.00]
430 435 440 445 450 455 460 465 470 475 480 485 490 495 500 505 510 515 520
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
R
el
at
iv
e 
A
bu
nd
an
ce
472.0189
z=1
474.0181
z=1
470.0199
z=1
476.0161
z=1
466.0229
z=1
479.5409
z=? 495.4157
z=?
503.9903
z=?
439.3537
z=?
429.9967
z=?
463.3043
z=?
455.0578
z=?
516.0448
z=?
445.0077
z=?
508.3331
z=?
491.0170
z=?
S3 
 
Figure S2: (+)ESI-MS (m/z) C2[(η6-p-cymene)Ru(L2-H)]+ Calculated 382.084664, found 382.0903, in 
MeOH + 0.1% TFA. 
 
 
 
 
 
 
 
 
 
S4 
 
Figure S3: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L1 
C1_1H NMR.esp
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Chemical Shift (ppm)
1.455.450.652.510.401.070.253.440.221.120.920.501.650.490.99
DMSO
8
.
8
9
0
8
.
8
7
9
8
.
5
9
2
8
.
3
5
5
8
.
3
3
7
8
.
1
6
9
8
.
0
9
9
8
.
0
9
5
7
.
7
6
7
7
.
7
6
2
7
.
7
4
8
7
.
7
4
4
5
.
8
2
2
5
.
8
0
9
5
.
7
7
9
5
.
7
6
6
5
.
5
5
6
5
.
5
4
4
3
.
3
6
6
3
.
1
6
7
2
.
8
5
9
2
.
8
4
5
2
.
8
3
1
2
.
8
1
7
2
.
8
0
3
2
.
1
0
6
2
.
0
8
6
2
.
0
1
8
1
.
7
9
6
1
.
1
9
8
1
.
1
8
4
1
.
1
3
4
1
.
1
2
6
1
.
1
2
0
1
.
1
1
2
L1_1H NMR.esp
8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6
Chemical Shift (ppm)
2.011.011.011.200.971.00
8
.
8
3
5
8
.
8
2
6
8
.
3
3
3
8
.
2
8
2
8
.
1
1
8
8
.
1
0
0
8
.
0
5
2
8
.
0
4
8
8
.
0
1
8
8
.
0
0
8
7
.
6
8
7
7
.
6
8
4
7
.
6
6
9
7
.
6
6
6
N
NH
Cl
S
NH2
L1
2
3
4
4a
5
6
7
8
8a
water
 
 
S5 
 
Figure S4: 13C{1H} NMR (125 MHz, DMSO-d6)spectrum of ligand L1 
L1_13C NMR.esp
230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
Chemical Shift (ppm)
3
9
.
0
1
1
3
9
.
1
7
7
3
9
.
3
4
3
3
9
.
5
0
9
3
9
.
6
7
5
3
9
.
8
4
1
4
0
.
0
1
5
1
1
5
.
6
8
5
1
2
1
.
5
9
1
1
2
4
.
7
3
9
1
2
6
.
6
5
2
1
2
7
.
7
9
3
1
3
4
.
1
9
1
1
4
3
.
2
3
8
1
4
9
.
1
3
0
1
5
1
.
7
8
7
1
8
2
.
2
0
6
L1_13C NMR.esp
150 148 146 144 142 140 138 136 134 132 130 128 126 124 122 120 118 116
Chemical Shift (ppm)
1
1
5
.
6
8
5
1
2
1
.
5
9
1
1
2
4
.
7
3
9
1
2
6
.
6
5
2
1
2
7
.
7
9
3
1
3
4
.
1
9
1
1
4
3
.
2
3
8
1
4
9
.
1
3
0
1
5
1
.
7
8
7
N
NH
Cl
S
NH2
L1
2
3
44a
5
6
7
8
8a
 
S6 
 
Figure S5: 1H NMR (200 MHz, DMSO-d6) spectrum of complex C1 
C1_1H NMR.esp
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0
Chemical Shift (ppm)
1.455.450.652.510.401.070.253.440.221.120.920.501.650.490.99
DMSO
1
.
1
1
2
1
.
1
2
0
1
.
1
2
6
1
.
1
3
4
1
.
1
8
4
1
.
1
9
8
1
.
7
9
6
2
.
0
1
8
2
.
0
8
6
2
.
1
0
6
2
.
8
0
3
2
.
8
1
7
2
.
8
3
1
2
.
8
4
5
2
.
8
5
9
3
.
1
6
7
3
.
3
6
6
5
.
5
4
4
5
.
5
5
6
5
.
7
6
6
5
.
7
7
9
5
.
8
0
9
5
.
8
2
2
7
.
7
4
4
7
.
7
4
8
7
.
7
6
2
7
.
7
6
7
8
.
0
9
9
8
.
3
3
7
8
.
3
5
5
8
.
5
9
2
8
.
8
7
9
8
.
8
9
0
C1_1H NMR.esp
8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6
Chemical Shift (ppm)
0.221.120.920.501.650.490.99
7
.
7
4
4
7
.
7
4
8
7
.
7
6
2
7
.
7
6
7
8
.
0
9
5
8
.
0
9
9
8
.
1
6
5
8
.
1
6
9
8
.
3
3
7
8
.
3
5
5
8
.
5
9
2
8
.
8
7
9
8
.
8
9
0
water
N
NH
Cl
S
NH2
Ru
Cl
C1
Cl
-
2
3
44a56
7
8
8a
9
10
11 12
1314 15
16'
16
11' 12'
 
 
S7 
 
Figure S6: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand C1 
C1_13C NMR.esp
230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
Chemical Shift (ppm)
1
7
.
6
9
1
1
7
.
8
4
2
1
8
.
4
4
9
2
1
.
4
7
4
2
2
.
1
7
4
2
3
.
9
6
5
2
9
.
9
4
4
3
0
.
8
1
7
3
9
.
0
1
2
3
9
.
1
7
9
3
9
.
3
4
5
3
9
.
5
1
1
3
9
.
6
7
7
3
9
.
8
4
3
4
0
.
0
0
9
7
9
.
0
2
8
8
0
.
7
0
3
8
5
.
4
8
3
8
6
.
3
3
5
1
0
0
.
0
6
1
1
0
0
.
6
1
0
1
0
6
.
3
5
0
1
1
3
.
3
1
1
1
2
0
.
5
0
2
1
2
5
.
2
1
0
1
2
7
.
1
9
6
1
2
8
.
7
7
7
1
3
5
.
5
5
7
1
4
5
.
9
6
1
1
4
9
.
3
7
7
1
8
2
.
0
2
7
C1_13C NMR.esp
145 140 135 130 125 120 115 110 105 100
Chemical Shift (ppm)
1
0
0
.
0
6
1
1
0
0
.
6
1
0
1
0
6
.
3
5
0
1
1
3
.
3
1
1
1
2
0
.
5
0
2
1
2
5
.
2
1
0
1
2
6
.
0
5
5
1
2
7
.
1
9
6
1
2
8
.
7
7
7
1
3
5
.
5
5
7
1
4
5
.
9
6
1
1
4
9
.
3
7
7
N
NH
Cl
S
NH2
Ru
Cl
C1
Cl
-
2
3
44a56
7
8
8a
9
10
11 12
1314 15
16'
16
11' 12'
 
 
 
 
S8 
 
Figure S7: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L1 
δH 9.22 (1H, br s, S=C-NH), 9.07 (1H, d, 3J(H2, H3) = 6.7 Hz, H2), 9.05 (1H, br s, S=C-NH), 8.99 (1H, d, 3J(H2, H3) = 6.7 Hz, H3), 8.81 (1H, d, 3J(H5, H6) = 
9.2 Hz, H5), 8.22 (1H, d, 4J(H6, H8) = 2.1 Hz, H8), 7.91 (1H, dd, 3J(H5, H6) = 9.2 Hz, 4J(H6, H8)  = 2.1 Hz, H6). 
L1_1H NMR_NH hsqc.esp
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
Chemical Shift (ppm)
1.000.970.971.051.900.90
DMSO
Water
9
.
2
1
5
9
.
0
7
6
9
.
0
6
3
8
.
9
9
9
8
.
9
8
5
8
.
8
1
6
8
.
7
9
7
8
.
2
1
9
7
.
9
2
0
7
.
9
1
6
7
.
9
0
2
L1_1H NMR_NH hsqc.esp
9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9
Chemical Shift (ppm)
1.000.970.971.051.900.90
9
.
2
1
5
9
.
0
7
6
9
.
0
6
3
9
.
0
4
6
8
.
9
9
9
8
.
9
8
5
8
.
8
1
6
8
.
7
9
7
8
.
2
1
9
8
.
2
1
5
7
.
9
2
0
7
.
9
1
6
7
.
9
0
2
N
NH
Cl
S
NH2
L1
2
3
4
4a
5
6
7
8
8a
 
S9 
 
Figure S8: 1H-15N HSQCNMR (500 MHz, DMSO-d6) spectrum of ligand L1 
L1_15N.999.001.2rr.esp
9.5 9.0 8.5 8.0
F2 Chemical Shift (ppm)
-250
-200
-150
-100
-50
0
50
100
150
200
250
300
350
400
450
500
550
600
650
F
1
 
C
h
e
m
i
c
a
l
 
S
h
i
f
t
 
(
p
p
m
)
15N 131.02 ppm
9
.
2
2
 
p
p
m
9
.
0
5
 
p
p
m
N
NH
Cl
S
NH2
L1
2
3
44a
5
6
7
8
8a
 
 
 
S10 
 
Figure S9: 1H NMR (500 MHz, DMSO-d6) spectrum of complex C1 
δH 8.90 (1H, d, 3J(H2, H3) = 5.5 Hz, H2), 8.67 (1H, bs S=C-NH), 8.57-8.47 (3H, m, H3, H5 and S=C-NH), 8.12 (1H, d, 4J(H6, H8) = 2.1 Hz, H8), 7.76 (1H, 
dd, 3J(H5, H6) = 9.0 Hz, 4J(H6, H8) = 2.3 Hz, H6), 5.73 - 5.84 (4H, m, H11, H11'', H12 and H12'), 2.88-2.76 (1H, m, H15), 2.08 (3H, s, H14), 1.19 (6H, d, 
3J(H15, H16) = 7.02 Hz, H16 and H16'). 
C1_1H NMR_NH hsqc.esp
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
3.867.101.243.251.564.551.361.002.921.181.44
M03(d)
M04(dd)
M06(d)
M01(d)
M07(dt)
M05(m)
M02(m)
1
.
1
0
8
1
.
1
2
2
1
.
1
8
0
1
.
1
9
4
2
.
0
2
1
2
.
0
8
3
2
.
1
0
4
2
.
2
4
2
2
.
5
4
0
2
.
5
5
4
2
.
8
0
0
2
.
8
1
4
2
.
8
2
7
2
.
8
4
1
2
.
8
5
5
3
.
1
6
4
5
.
5
5
8
5
.
5
7
0
5
.
7
6
4
5
.
7
7
7
5
.
8
0
5
5
.
8
1
8
7
.
7
4
5
7
.
7
5
0
7
.
7
6
3
7
.
7
6
7
7
.
7
7
4
7
.
7
7
8
8
.
1
2
2
8
.
1
2
6
8
.
2
3
8
8
.
5
0
1
8
.
5
1
2
8
.
5
2
0
8
.
6
7
2
8
.
8
9
0
8
.
9
0
1
C1_1H NMR_NH hsqc.esp
8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8
Chemical Shift (ppm)
1.361.002.911.181.44
8
.
9
0
1
8
.
8
9
0
8
.
6
7
2
8
.
5
2
0
8
.
5
0
1
8
.
2
3
8
8
.
2
3
3
8
.
1
2
6
8
.
1
2
2
7
.
7
7
8
7
.
7
7
4
7
.
7
6
7
7
.
7
6
3
7
.
7
5
0
7
.
7
4
5
DMSO
N
NH
Cl
S
NH2
Ru
Cl
C1
Cl
-
2
3
44a56
7
8
8a
9
10
11 12
1314 15
16'
16
11' 12'
 
 
 
S11 
 
Figure S10: 1H-15N HSQC NMR (500 MHz, DMSO-d6) spectrum of complex C1 (selected part of spectrum) 
C1_N-hsqc NMR.esp
9.0 8.5 8.0 7.5
F2 Chemical Shift (ppm)
-250
-200
-150
-100
-50
0
50
100
150
200
250
300
350
400
F
1
 
C
h
e
m
i
c
a
l
 
S
h
i
f
t
 
(
p
p
m
)
15N 122.24 ppm
8
.
6
7
 
p
p
m
8
.
5
7
-
8
.
4
7
 
p
p
m
N
NH
Cl
S
NH2
Ru
Cl
C1
Cl
-
2
3
44a56
7
8
8a
9
10
11 12
1314 15
16'
16
11' 12'
 
S12 
 
Figure S11: 1H NMR (200 MHz,DMSO-d6) spectrum of ligand L2xHCl 
L2xHCl_1H NMR.esp
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Chemical Shift (ppm)
4.134.380.961.000.980.952.00
3
.
9
5
5
4
.
0
1
1
6
.
1
6
5
7
.
7
7
7
7
.
8
0
2
7
.
8
1
9
7
.
8
4
1
8
.
7
0
6
8
.
7
1
5
8
.
7
2
3
8
.
7
5
7
8
.
7
6
5
8
.
9
4
2
8
.
9
6
5
9
.
3
9
2
1
1
.
4
6
1
L2xHCl_1H NMR.esp
9.5 9.0 8.5 8.0
Chemical Shift (ppm)
0.961.000.980.95
7
.
7
7
7
7
.
8
0
2
7
.
8
1
9
7
.
8
4
1
8
.
7
0
6
8
.
7
1
5
8
.
7
2
3
8
.
7
4
6
8
.
7
5
7
8
.
7
6
5
8
.
9
4
2
8
.
9
6
5
9
.
3
9
2
N
N
N
H x HCl
L2xHCl
2
3
4
5
6
7
8
9
DMSO
 
 
S13 
 
Figure S12: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand L2xHCl 
L2xHCl_13C NMR.esp
240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40
Chemical Shift (ppm)
1
6
2
.
8
8
5
1
5
3
.
3
0
8
1
4
8
.
3
9
3
1
3
8
.
4
7
0
1
2
4
.
9
0
6
1
1
9
.
8
6
3
4
4
.
6
8
6
4
0
.
9
7
2
4
0
.
5
3
5
4
0
.
1
3
5
3
9
.
7
1
6
3
9
.
2
9
7
3
8
.
8
7
8
3
8
.
4
6
0
L2xHCl_13C NMR.esp
160 155 150 145 140 135 130 125 120 115
Chemical Shift (ppm)
1
6
2
.
8
8
5
1
5
3
.
3
0
8
1
4
8
.
3
9
3
1
3
8
.
4
7
0
1
2
4
.
9
0
6
1
1
9
.
8
6
3
N
N
N
H x HCl
L2xHCl
2
3
4
5
6
7
8
9
 
S14 
 
Figure S13: 1H NMR (200 MHz, DMSO-d6) spectrum of complex C2 
C2_1H NMR.esp
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
6.983.201.924.064.204.538.658.671.081.190.821.002.27
Water
1
0
.
7
0
5
9
.
0
9
6
9
.
0
8
5
8
.
9
1
9
8
.
9
1
4
8
.
8
9
7
8
.
8
8
8
8
.
3
1
5
8
.
3
0
7
8
.
2
9
6
8
.
2
7
6
8
.
2
6
8
8
.
2
5
6
8
.
2
4
2
7
.
7
1
2
7
.
6
8
6
7
.
6
7
0
7
.
6
4
7
7
.
2
0
1
7
.
0
2
4
6
.
9
6
2
6
.
9
2
8
6
.
8
8
9
6
.
7
8
5
6
.
7
5
1
5
.
8
1
9
5
.
7
8
5
5
.
7
7
7
5
.
7
4
3
4
.
1
2
3
4
.
0
6
4
4
.
0
2
7
3
.
9
2
9
3
.
4
9
1
3
.
2
9
7
2
.
9
0
4
2
.
8
7
0
2
.
8
3
4
2
.
8
0
0
2
.
2
1
0
2
.
1
1
5
2
.
0
1
6
1
.
3
2
8
1
.
2
8
9
1
.
2
3
3
1
.
1
9
9
1
.
1
3
5
1
.
1
0
1
C2_1H NMR.esp
9.0 8.5 8.0 7.5 7.0
Chemical Shift (ppm)
4.538.658.671.081.190.821.00
9
.
0
9
6
9
.
0
8
5
8
.
9
1
9
8
.
9
1
4
8
.
8
9
7
8
.
8
8
8
8
.
3
1
5
8
.
3
0
7
8
.
2
9
6
8
.
2
7
6
8
.
2
6
8
8
.
2
5
6
8
.
2
4
2
7
.
7
1
2
7
.
6
8
6
7
.
6
7
0
7
.
6
4
7
7
.
2
0
1
7
.
0
2
4
6
.
9
6
2
6
.
9
2
8
6
.
8
8
9
6
.
8
2
1
6
.
7
8
5
6
.
7
5
1
N
Cl
Ru
ClNH
+
NH
C2
BPh4
-
10
11 12
1314 15
16'
16
11' 12'
2
3
4
5
6
7
8
9
DMSO
 
S15 
 
Figure S14: 13C{1H} NMR (50 MHz, DMSO-d6) spectrum of ligand C2 
C2_13C NMR.esp
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
Chemical Shift (ppm)
1
8
.
0
6
8
2
1
.
6
9
1
3
0
.
1
7
6
3
8
.
4
6
0
3
8
.
8
7
8
3
9
.
2
9
7
3
9
.
7
1
6
4
0
.
1
3
5
4
0
.
5
5
3
4
0
.
9
5
4
4
4
.
7
9
6
8
5
.
7
4
3
8
6
.
5
9
9
1
0
0
.
3
2
7
1
0
6
.
6
0
8
1
1
9
.
2
6
2
1
2
1
.
7
7
4
1
2
4
.
3
7
8
1
2
5
.
4
7
0
1
2
5
.
5
7
9
1
2
5
.
6
3
4
1
3
5
.
7
9
4
1
3
6
.
4
1
3
1
4
9
.
1
9
4
1
5
5
.
0
3
8
1
6
2
.
1
3
9
1
6
3
.
1
2
2
1
6
3
.
9
0
5
1
6
4
.
1
0
5
1
6
5
.
0
8
8
C2_13C NMR.esp
165 160 155 150 145 140 135 130 125 120
Chemical Shift (ppm)
1
1
9
.
2
6
2
1
2
1
.
7
7
4
1
2
4
.
3
7
8
1
2
5
.
4
7
0
1
2
5
.
5
2
5
1
2
5
.
5
7
9
1
2
5
.
6
3
4
1
3
5
.
7
5
7
1
3
5
.
7
9
4
1
3
6
.
4
1
3
1
4
9
.
1
9
4
1
5
5
.
0
3
8
1
6
2
.
1
3
9
1
6
3
.
1
2
2
1
6
3
.
9
0
5
1
6
4
.
1
0
5
1
6
5
.
0
8
8
N
Cl
Ru
ClNH
+
NH
C2
BPh4
-
10
11 12
1314 15
16'
16
11' 12'
2
3
4
5
6
7
8
9
 
S16 
 
Figure S15: 1H NMR (500 MHz, DMSO-d6) spectrum of ligand L2 (as base) 
δH 9.29 (1H, d, 3J(H2, H4) = 1.7 Hz, H2), 8.77 (1H, d, 3J(H5, H6) = 4.5 Hz, 4J(H4, H6) = 1.5 Hz, H6), 8.57 (1H, dt, 3J(H4, H5) = 8.2 Hz, 3J(H2, H4) = 1.8 Hz, H4), 
7.58 (1H, ddd, 3J(H4, H5) = 8.1 Hz, 3J(H5, H6) = 4.9 Hz, J = 0.7 Hz, H5), 3.85 (4H, s, H8 and H9). 
L2_1H NMR_NH hmbc.esp
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Chemical Shift (ppm)
0.580.130.393.980.981.000.971.00
9
.
2
9
1
8
.
7
7
9
8
.
7
7
6
8
.
7
6
9
8
.
5
7
8
8
.
5
7
5
8
.
5
5
8
8
.
5
5
4
7
.
5
9
3
7
.
5
8
3
7
.
5
8
2
7
.
5
7
7
7
.
5
6
7
7
.
5
6
6
3
.
8
5
2
3
.
4
0
8
3
.
3
9
4
3
.
3
8
0
3
.
3
6
6
3
.
0
7
6
2
.
5
0
3
2
.
5
0
0
1
.
0
1
5
1
.
0
0
1
0
.
9
8
7
L2
N
N
N
H2
3
4
5
6
7
8
9
DMSO Et3N
Et3N
L2_1H NMR_NH hmbc.esp
9.0 8.5 8.0 7.5
Chemical Shift (ppm)
0.981.000.971.00
9
.
2
9
4
9
.
2
9
1
8
.
7
7
9
8
.
7
7
6
8
.
7
6
9
8
.
7
6
6
8
.
5
7
8
8
.
5
7
5
8
.
5
7
1
8
.
5
6
2
8
.
5
5
8
8
.
5
5
4
7
.
5
9
3
7
.
5
9
1
7
.
5
8
3
7
.
5
8
2
7
.
5
7
7
7
.
5
7
5
 
 
 
S17 
 
Figure S16: 1H-15N HMBC NMR (500 MHz, DMSO-d6) spectrum of ligand L2 
L2_N-hmbc NMR.esp
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
F2 Chemical Shift (ppm)
0
50
100
150
200
250
300
350
400
450
500
F
1
 
C
h
e
m
i
c
a
l
 
S
h
i
f
t
 
(
p
p
m
)
15N 316.7 ppm
9
.
2
9
 
p
p
m
8
.
7
7
 
p
p
m
3
.
8
5
 
p
p
m
15N 251.0 ppm
15N 127.73 ppm
L2
N
N
N
H2
3
4
5
6
7
8
9
 
 
S18 
 
Figure S17: 1H NMR (500 MHz, DMSO-d6) spectrum of complex C2:  
δH 9.08 (1H, d, 3J(H2, H4) = 1.9 Hz, H2), 8.90 (1H, dd, 3J(H5, H6) = 4.8 Hz, 3J(H4, H6) = 1.5 Hz, H6), 8.29 (1H, dt, 3J(H4, H5) = 8.0 Hz, 3J(H2, H4)  = 2.0 Hz, H4), 
7.70 (1H, ddd, 3J(H4, H5) = 8.8 Hz, 3J(H5, H6) = 4.8 Hz, J = 0.7 Hz, H5), 7.21-7.15 (8H, m, H2-BPh4), 6.92 (8H, t, 3J(H2ʼ, H3ʼ, H4ʼ) = 7.4 Hz, H3-BPh4), 6.82-
6.76 (4H, m, H4-BPh4), 5.84-5.75 (4H, m, H11, H11'', H12 and H12'), 4.0 (4H, s, H8 and H9), 2.88-2.78 (1H, m, H15), 2.09 (3H, s, H14), 1.19 (6H, d, 
3J(H15, H16) = 7.0 Hz, H16 and H16'). 
N
Cl
Ru
ClNH
+
NH
C2
BPh4
-
10
11 12
1314 15
16'
16
11' 12'
2
3
4
5
6
7
8
9
C2_1H NMR_NH hmbc.esp
9.0 8.5 8.0 7.5 7.0
Chemical Shift (ppm)
1.232.452.400.270.270.250.26
6
.
7
7
4
6
.
7
8
8
6
.
8
0
3
6
.
9
0
8
6
.
9
2
3
6
.
9
3
8
7
.
1
6
7
7
.
1
7
0
7
.
1
7
7
7
.
1
8
0
7
.
1
8
5
7
.
1
8
8
7
.
1
9
0
7
.
1
9
3
7
.
6
8
4
7
.
6
9
2
7
.
6
9
4
7
.
6
9
9
7
.
7
0
0
7
.
7
0
8
7
.
7
1
0
8
.
2
7
7
8
.
2
8
1
8
.
2
8
5
8
.
2
9
3
8
.
2
9
7
8
.
3
0
1
8
.
8
9
3
8
.
8
9
6
8
.
9
0
2
8
.
9
0
6
9
.
0
8
1
9
.
0
8
4
C2_1H NMR_NH hmbc.esp
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
Chemical Shift (ppm)
1.650.810.340.301.071.161.232.452.400.270.270.250.26
DMSO
Water
1
.
1
5
5
1
.
1
8
7
1
.
2
0
1
1
.
2
3
5
1
.
2
4
9
2
.
0
8
7
2
.
8
0
6
2
.
8
2
0
2
.
8
3
4
2
.
8
4
7
3
.
0
5
0
3
.
0
6
5
3
.
0
7
9
3
.
0
9
4
3
.
1
7
2
3
.
9
3
2
3
.
9
9
7
5
.
7
6
3
5
.
7
7
6
5
.
8
0
8
5
.
8
2
1
6
.
7
7
4
6
.
7
8
8
6
.
9
0
8
6
.
9
2
3
6
.
9
3
8
7
.
1
7
0
7
.
1
7
7
7
.
1
8
5
7
.
1
9
0
7
.
1
9
6
7
.
6
8
4
7
.
6
9
2
7
.
6
9
4
7
.
6
9
9
7
.
7
0
8
7
.
7
1
0
8
.
2
7
7
8
.
2
8
1
8
.
2
8
5
8
.
2
9
3
8
.
2
9
7
8
.
3
0
1
8
.
8
9
6
8
.
9
0
2
8
.
9
0
6
9
.
0
8
1
9
.
0
8
4
Et3N
Et3N
 
S19 
 
 
Figure S18: 1H-15N HMBC NMR (500 MHz, DMSO-d6) spectrum of complex C2 (selected part of spectrum) 
C2_N-hmbc NMR.esp
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
F2 Chemical Shift (ppm)
0
50
100
150
200
250
300
350
400
450
500
F
1
 
C
h
e
m
i
c
a
l
 
S
h
i
f
t
 
(
p
p
m
)
9
.
0
8
 
p
p
m
8
.
9
0
 
p
p
m
4
.
0
 
p
p
m
15N 317.65 ppm
15N 115.33 ppm
N
Cl
Ru
ClNH
+
NH
C2
BPh4
-
10
11 12
1314 15
16'
16
11' 12'
2
3
4
5
6
7
8
9
 
S20 
 
Figure S19. Stability of complex C1 in 24h period; 1H NMR spectra were recorded in DMSO-
d6: a) ligand region; b) p-cymene region. 
 
a) 
  
b) 
 
       
 
S21 
 
Figure S20. Stability of complex C2 in 24 h period; 1H NMR spectra were recorded in DMSO-
d6:  a) ligand region; b) p-cymene region. 
 
a) 
 
b) 
 
      
S22 
 
Figure S21. Comparison of 1H NMR spectrum of complex C1 after 24 h period and 1H NMR 
spectrum of free ligand L1. Spectra were recorded in DMSO-d6. 
 
Figure S22. Comparison of 1H NMR spectrum of complex C2 after 24 h period and 1H NMR 
spectrum of free ligand L2. Spectra were recorded in DMSO-d6. 
 
 
S23 
 
Figure S23. Comparison of 1H NMR spectrum of complex C1 after 24 h period and 1H NMR 
spectrum of complex [Ru(cymene)Cl2DMSO]. Spectra were recorded in DMSO-d6. 
 
 
 
Figure S24. Comparison of 1H NMR spectrum of complex C2 after 24 h period and 1H NMR 
spectrum of complex [Ru(cymene)Cl2DMSO]. Spectra were recorded in dmso-d6. 
 
S24 
 
Figure S25: Cell survival after 72h treatment of A549 cell line with ligands L1, L2, complexes 
C1, C2 and CDDP. 
 
Figure S26:Cell survival after 72h treatment of HeLa cell line with ligands L1, L2, complexes 
C1, C2 and CDDP  
 
Figure S27: Cell survival after 72h treatment of MDA-MB-231 cell line with ligands L1, L2, 
complexes C1, C2 and CDDP 
 
 


English

http://cherry.chem.bg.ac.rs/bitstream/id/14978/Strong_in_Vitro_sup_2015.pdf

キンセイジョウシユライノトシコウエンニオケルシゼンリョクチノセイタイテキ・シャカイテキヒョウカ

Abstract

Similar works

Full text

Available Versions

Tokushima University Institutional Repository

Faculty of Chemistry Repository - Cherry

Cherry - Repository of the Faculty of Chemistry; University of Belgrade

キンセイ ジョウシ ユライ ノ トシ コウエン ニオケル シゼン リョクチ ノ セイタイテキ・シャカイテキ ヒョウカ

Abstract

Similar works

Full text

Available Versions

Tokushima University Institutional Repository

Faculty of Chemistry Repository - Cherry

Cherry - Repository of the Faculty of Chemistry; University of Belgrade

キンセイジョウシユライノトシコウエンニオケルシゼンリョクチノセイタイテキ・シャカイテキヒョウカ