Inorganic Chemistry H5d), 5.99 (t, 1H, J = 5.67 Hz, H3d), 4.59 (s, 2H, H10d), 4.34 (tr, 2H, J = 4.62 Hz, H7d). 13C NMR (125.81 MHz, DMSO-d6): δ 191.83 (C17d), 168.09 (C9d), 162.69 (C11d), 153.61 (C8a), 150.73 (C6a), 146.74 (C2b), 141.41 (C9b), 134.90 (C3a), 134.58 (C8b), 132.12 (C13d + C15d), 131.51 (C4a), 130.62 (C14d), 125.35 (C5b or C6b), 124.89 (C5b or C6b), 119.38 (C5a), 117.84 (C4b), 115.66 (C12d + C16d), 113.90 (C7b), 111.76 (C9a), 101.93 (C6d), 85.39 (C2d or C4d), 85.09 (C2d or C4d), 83.92 (C3d), 82.67 (C1d or C5d), 82.31 (C1d or C5d), 67.19 (C10d), 40.46 (C7d). 15N NMR (50.70 MHz, DMSO-d6): δ 89.5 (N8d). Orange crystals of cis,cis-[RuIICl2(DMSO)2(L1)]·H2O suitable for X- ray diffraction study were grown by recrystallization from ethanol of the product, obtained by the slow evaporation (2−3 months) of a DMSO solution of 1c. Synthesis of [RuCl(η6-arene)(L2)]Cl (2c). a. Synthesis of 2c−HCl·H2O. [RuCl(μ-Cl)(η6-arene)]2·0.5H2O (100 mg, 0.11 mmol) and L2 (80 mg, 0.26 mmol) were heated in ethanol (20 mL) at 85 °C for 1.5 h. The solvent was evaporated to half of the initial volume, and the yellow precipitate of [RuCl(η6-arene)(L2−H)] (2c−HCl) was removed by filtration and dried in vacuo at 50 °C. Yield: 151.8 mg, 92%. Anal. Calcd for C29H22BrClN6O3Ru·H2O (2c−HCl·H2O) (Mr = 736.97 g mol−1): C, 47.26; H, 3.28; N, 11.40; Cl, 4.81; Br, 10.84. Found: C, 47.53; H, 2.97; N, 11.16; Cl, 4.90; Br, 11.04. ESI-MS in MeOH (positive): m/z 721 [2c−HCl + H]+, 743 [2c−HCl + Na]+. ESI- MS in MeOH (negative): m/z 719 [2c−HCl − H]−. 1H NMR (500.32 MHz, DMSO-d6): δ 13.89 (br s, 1H, H1b), 9.87 (s, 1H, H17d), 9.03 (tr, 1H, J = 5.96 Hz, H8d), 8.99 (d, 1H, J = 2.06 Hz, H4a), 8.55 (d, 1H, J = 2.04 Hz, H6a), 8.01 (d, 1H, J = 8.02 Hz, H4b), 7.84 (d, 2H, J = 8.76 Hz, H13d + H15d), 7.72 (d, 1H, J = 7.54 Hz, H7b), 7.47 (tr, 1H, J = 7.11 Hz, H5b or H6b), 7.43 (tr, 1H, J = 7.14 Hz, H5b or H6b), 7.13 (d, 2H, J = 8.69 Hz, H12d + H16d), 6.39 (tr, 1H, J = 5.79 Hz, H2d or H4d), 6.25 (d, 1H, J = 5.81 Hz, H1d or H5d), 6.14 (tr, 1H, J = 5.39 Hz, H2d or H4d), 6.06 (m, 2H, H1d or H5d + H3d), 4.75 (dd, 2H, J = 14.49 and 25.44 Hz, H10d), 4.42 (d, 2H, J = 5.94 Hz, H7d). The yellow crystals of mer- [RuIICl(DMSO)3(L2-H)]·H2O suitable for X-ray diffraction study were grown from a EtOH/H2O solution of the product, obtained by the slow evaporation (2 months) of a DMSO solution of 2c−HCl. b. Synthesis of 2c·0.5H2O. A total of 37% HCl (24 mg) was added to 2c−HCl·H2O (130 mg, 0.18 mmol) in ethanol (20 mL). The suspension was stirred at room temperature for 1 h, and the solvent was removed under reduced pressure. The residue (2c) was suspended in diethyl ether, collected by filtration, and dried in vacuo at 50 °C. Yield: 135 mg, 100%. Anal. Calcd for C29H23BrCl2N6O3Ru·0.5H2O (2c·0.5H2O) (Mr = 764.42 g mol−1): C, 45.57; H, 3.16; N, 10.99; Cl, 9.28. Found: C, 45.75; H, 2.86; N, 10.86; Cl, 8.75. ESI-MS in MeOH (positive): m/z 743 [2c − HCl + Na]+. ESI-MS in MeOH (negative): m/z 719 [2c − HCl − H]−. UV−vis [MeOH; λmax, nm (ε, M−1 cm−1)]: 256 (18 146), 300 (24 730), 360 (10 018). 1H NMR (500.32 MHz, DMSO-d6): δ 14.42 (br s, 1H, H1b), 9.88 (s, 1H, H17d), 9.22 (br s, 1H, H4a), 8.88 (tr, 1H, J = 5.77 Hz, H8d), 8.70 (br s, 1H, H6a), 8.06 (d, 1H, J = 7.23 Hz, H4b), 7.84 (d, 2H, J = 8.83 Hz, H13d + H15d), 7.78 (dd, 1H, J = 1.4 and 7.27 Hz, H7b), 7.50 (m, 2H, H5b + H6b), 7.08 (d, 2H, J = 8.75 Hz, H12d + H16d), 6.46 (tr, 1H, J = 5.76 Hz, H2d or H4d), 6.39 (d, 1H, J = 6.35 Hz, H1d or H5d), 6.35 (tr, 1H, J = 4.21 Hz, H2d or H4d), 6.23 (d, 1H, J = 5.63 Hz, H1d or H5d), 6.04 (t, 1H, J = 5.49 Hz, H3d), 4.63 (dd, 2H, J = 14.34 and 18.53 Hz, H10d), 4.35 (ddd, 2H, J = 6.06, 15.03, and 22.65 Hz, H7d). 13C NMR (125.81 MHz, DMSO-d6): δ 191.81 (C17d), 168.07 (C9d), 162.68 (C11d), 155.35 (C8a), 150.43 (C6a), 147.32 (C2b), 141.46 (C9b), 134.49 (C8b), 133.23 (C3a), 132.11 (C13d + C15d), 131.16 (C4a), 130.63 (C14d), 125.05 (C5b or C6b), 124.70 (C5b or C6b), 117.64 (C4b), 115.66 (C12d + C16d), 114.25 (C5a or C9a), 113.66 (C7b), 112.69 (C5a or C9a), 101.19 (C6d), 85.26 (C2d or C4d), 84.51 (C2d or C4d), 83.97 (C3d), 83.04 (C1d or C5d), 82.79 (C1d or C5d), 67.19 (C10d), 40.30 (C7d). 15N NMR (50.70 MHz, DMSO- d6): δ 123.7 (N1b), 88.6 (N8d). Synthesis of [RuCl(η6-arene)(L3)]Cl (3c). [RuCl(μ-Cl)(η6-are- ne)]2·0.5H2O (100 mg, 0.11 mmol) and L3 (91.5 mg, 0.26 mmol) were heated in ethanol (20 mL) at 85 °C for 1 h. The solvent was evaporated to one-third of the initial volume, and the yellow precipitate (3c) that formed was removed by filtration and dried in vacuo at 50 °C. Yield: 166 mg, 90%. Anal. Calcd for Article C31H27BrCl2N6O4Ru·1.5H2O (3c·1.5H2O) (Mr = 826.49 g mol−1): C, 45.05; H, 3.66; N, 10.17; Cl, 8.58; Br, 9.67. Found: C, 45.31; H, 3.24; N, 10.06; Cl, 8.30; Br, 9.36. ESI-MS in MeOH (positive): m/z 727 [3c − HCl − Cl]+, 749 [3c − 2HCl + Na]+, 765 [3c − Cl]+, 785 [3c − HCl + Na]+. ESI-MS in MeOH (negative): m/z 726 [3c − 2HCl − H]−, 763 [3c − HCl − H]−. UV−vis [MeOH; λmax, nm (ε, M−1 cm−1)]: 259 (29 157), 302 (37 725), 361 (16 424). 1H NMR (500.32 MHz, DMSO-d6): δ 14.03 (br s, 1H, H1b), 9.88 (s, 1H, H17d), 9.46 (s, 1H, H4a), 8.88 (tr, 1H, J = 5.65 Hz, H8d), 8.69 (d, 1H, J = 1.74 Hz, H6a), 8.01 (d, 1H, J = 7.85 Hz, H4b), 7.84 (d, 2H, J = 8.81 Hz, H13d + H15d), 7.49 (m, 2H, H5b + H6b), 7.07 (d, 2H, J = 8.68 Hz, H12d + H16d), 6.45 (tr, 1H, J = 5.65 Hz, H2d or H4d), 6.39 (d, 1H, J = 6.08 Hz, H1d or H5d), 6.34 (tr, 1H, J = 4.46 Hz, H2d or H4d), 6.23 (d, 1H, J = 6.05 Hz, H1d or H5d), 6.03 (tr, 1H, J = 5.54 Hz, H3d), 4.87 (dd, 2H, J = 12.39 and 16.13 Hz, H10b), 4.63 (dd, 2H, J = 14.74 and 21.11 Hz, H10d), 4.35 (ddd, 2H, J = 5.88, 15.17, and 19.74 Hz, H7d), 3.39 (s, 3H, H11b). 13C NMR (125.81 MHz, DMSO-d6): δ 191.81 (C17d), 168.03 (C9d), 162.65 (C11d), 154.91 (C8a), 150.59 (C6a), 147.44 (C2b), 141.69 (C9b), 133.23 (C3a), 132.98 (C8b), 132.10 (C13d + C15d), 131.78 (C4a), 130.62 (C14d), 124.91 (C5b or C6b), 124.63 (C5b or C6b), 124.54 (C7b), 117.22 (C4b), 115.65 (C12d + C16d), 114.31 (C5a or C9a), 112.74 (C5a or C9a), 101.36 (C6d), 85.24 (C2d or C4d), 84.56 (C2d or C4d), 84.34 (C3d), 83.26 (C1d or C5d), 82.99 (C1d or C5d), 70.13 (C10b), 67.17 (C10d), 57.97 (C11b), 40.30 (C7d). 15N NMR (50.70 MHz, DMSO-d6): δ 123.8 (N1b), 88.9 (N8d). Synthesis of [RuCl(η6-arene)(L4)]Cl (4c). [RuCl(μ-Cl)(η6-are- ne)]2·0.5H2O (100.3 mg, 0.11 mmol) and L4 (80.03 mg, 0.23 mmol) were heated in ethanol (15 mL) at 85 °C for 3 h. After cooling to room temperature, the reaction mixture was filtered and evaporated to a minimum volume. The addition of diethyl ether resulted in the precipitation of a brown product, which was removed by filtration and d r i e d i n v a c u o . Y i e l d : 1 6 3 m g , 8 7 % . A n a l . C a l c d f o r C38H31Cl2N5O4Ru·2H2O (4c·2H2O) (Mr = 829.69 g mol−1): C, 55.01; H, 4.25; N, 8.44. Found: C, 55.04; H, 4.10; N, 8.41. ESI-MS in MeOH (positive): m/z 758 [4c − Cl]+, 723 [4c − HCl − Cl]+. ESI- MS in MeOH (negative): m/z 756 [4c − HCl − H]−, 720 [4c − 2HCl − H]−. UV−vis [MeOH; λmax, nm (ε, M−1 cm−1)]: 218 (63 208), sh 251 (42 884), sh 261 (42 361), sh 281 (36 827), sh 289 (35 680), 315 (33 347), 375 (12 616). UV−vis [H2O; λmax, nm (ε, M−1 cm−1)]: sh 216 (54 985), 288 (35 202), sh 313 (27 554), 381 (10 800). 1H NMR (500.32 MHz, DMSO-d6): δ 12.08 (s, 1H, H12′), 10.21 (s, 1H, H5′), 9.87 (s, 1H, H17d), 9.61 (d, 1H, J = 5.25 Hz, H18′), 8.98 (s, 1H, H14′), 8.78 (t, 1H, J = 5.94 Hz, H8d), 8.32−8.27 (m, 2H, H15′ + H16′), 8.08 (d, 1H, J = 1.93 Hz, H8′), 7.85 (d, 2H, J = 8.84 Hz, H13d + H15d), 7.84 (m, 1H, H1′ or H17′), 7.80 (dd, 1H, J = 1.15 and 7.73 Hz, H1′ or H17′), 7.77 (dd, 1H, J = 2.05 and 8.64 Hz, H10′), 7.64 (d, 1H, J = 8.66 Hz, H11′), 7.44 (t, 1H, J = 7.77 Hz, H3′), 7.32 (m, 2H, H2′ + H4′), 7.11 (d, 2H, J = 8.72 Hz, H12d + H16d), 6.17 (t, 1H, J = 5.96 Hz, H3d), 5.95−5.91 (m, 2H, H2d + H4d), 5.76−5.71 (m, 2H, H1d + H5d), 4.69 (dd, 2H, J = 14.94 and 20.42 Hz, H10d), 4.29 (ddd, 2H, J = 5.74, 15.36, and 33.98 Hz, H7d), 3.61 (s, 2H, H7′). 13C NMR (DMSO-d6, 125.81 MHz): δ 191.78 (C17d), 171.94 (C6′), 168.25 (C9d), 166.55 (C14′), 162.83 (C11d), 156.61 (C18′), 155.53 (C14a′), 145.69 (C9′), 140.41 (C16′), 138.08 (C11a′), 136.19 (C4a′), 135.43 (C12a′), 132.16 (C13d + C15d), 130.66 (C14d), 129.76 (C15′), 129.05 (C3′), 128.75 (C17′), 127.58 (C1′), 126.68 (C7b′), 124.29 (C2′), 122.89 (C4′), 122.83 (C12b′), 118.86 (C10′), 115.69 (C12d + C16d), 112.55 (C11′), 111.22 (C8′), 108.91 (C7a′), 102.16 (C6d), 88.49 (C1d or C5d), 88.37 (C3d), 85.86 (C2d or C4d; C1d or C5d), 85.80 (C2d or C4d; C1d or C5d), 85.11 (C2d or C4d), 67.28 (C10d), 39.93 (C7d), 32.32 (C7′). 15N NMR (DMSO-d6, 50.70 MHz): δ 116.38 (N5′), 110.02 (N12′), 88.51 (N8d). Synthesis of [RuCl(η6-arene)(L5)]Cl (5c). [RuCl(μ-Cl)(η6-are- ne)]2·0.5H2O (108 mg, 0.12 mmol) and L5 (102.3 mg, 0.25 mmol) were heated in ethanol (15 mL) at 85 °C for 3 h. After cooling to room temperature, the reaction mixture was filtered and evaporated to a minimum volume. Diethyl ether was added, and the yellow-brown precipitate was collected and dried in vacuo. Yield: 185 mg, 87%. Anal. Calcd for C38H32BrCl2N5O3Ru·H2O (5c·H2O) (Mr = 876.59 g mol−1): C, 52.07; H, 3.91; N, 7.99. Found: C, 51.97; H, 3.95; N, 7.73. ESI-MS in MeOH (positive): m/z 825 [5c − Cl]+, 789 [5c − 12671 dx.doi.org/10.1021/ic201801e | Inorg. Chem. 2011, 50, 12669−12679