Inorganic Chemistry Table 1. Crystal Data and Details of Data Collection for [RuCl2(η6-arene)(DMSO)]·0.5H2O, L2·DMSO, cis,cis- [RuIICl2(DMSO)2(L1)]·H2O, and mer-[RuIICl(DMSO)3(L2−H)]·H2O Article [RuCl2(η6-arene)DMSO]·0.5H2O [RuIICl2(DMSO)2(L1)]·H2O [RuIICl(DMSO)3(L2−H)]·H2O L2·DMSO C15H14BrN5OS 392.28 P21/c 8.5399(4) 10.2371(6) 18.5633(11) 94.712(4) 1617.39(15) 4 0.710 73 1.611 0.38 × 0.14 × 0.08 100 2.682 0.0428 0.0978 0.965 C17H23Cl2N5O3RuS2 581.49 P1̅ 7.8726(6) 11.1638(9) 13.0422(10) 97.546(5) 94.461(5) 106.202(5) 1083.29(15) 2 0.710 73 1.194 0.10 × 0.08 × 0.08 100 1.194 0.0519 0.1390 1.005 C19H27BrClN5O4RuS3 702.07 P21/c 11.8408(9) 12.9306(10) 17.9286(2) 108.707(4) 2600.0(3) 4 0.710 73 2.520 0.20 × 0.10 × 0.01 100 2.520 0.0355 0.0817 0.994 empirical formula fw space group a [Å] b [Å] c [Å] α [deg] β [deg] γ [deg] V [Å3] Z λ [Å] ρcalcd [g cm−3] cryst size [mm3] T [K] μ [mm−1] R1a wR2b GOFc C18H22Cl2NO4.5RuS 528.40 P1̅ 8.5676(4) 10.8811(4) 11.4797(5) 72.819(2) 89.461(3) 77.030(2) 994.49(7) 2 0.710 73 1.765 0.20 × 0.04 × 0.02 100 1.189 0.0461 0.1264 1.094 aR1 = ∑||Fo| − |Fc||/∑|Fo|. bwR2 = {∑[w(Fo2 − Fc2)2]/∑[w(Fo2)2]}1/2. cGOF = {∑[w(Fo2 − Fc2)2]/(n − p)}1/2, where n is the number of reflections and p is the total number of parameters refined. HCl − Cl]+. ESI-MS in MeOH (negative): m/z 823 [5c − HCl − H]−, 786 [5c − 2HCl − H]−. UV−vis [MeOH; λmax, nm (ε, M−1 cm−1)]: sh 230 (43 177), 268 (44 722), 319 (21 929). UV−vis [H2O; λmax, nm (ε, M−1 cm−1)]: sh 217 (32 402), sh 237 (26 864), 273 (28 107), 314 (13 462). a. NMR Characterization of E/Z Isomers in DMSO-d6. 1H NMR (500.32 MHz, DMSO-d6): E-isomer, δ 12.05 (s, 1H, H12′), 9.87 (s, 1H, H17d), 9.11 (d, 1H, J = 5.56 Hz, H18′), 9.07 (s, 1H, H5′), 8.69 (t, 1H, J = 5.9 Hz, H8d), 8.22 (d, 1H, J = 1.66 Hz, H8′), 8.09 (t, 1H, J = 7.86 Hz, H16′), 7.85 (d, 2H, J = 8.42 Hz, H13d + H15d), 7.83 (d, 1H, J = 7 Hz, H1′), 7.65 (d, 1H, J = 7.87 Hz, H15′), 7.59 (t, 1H, J = 6.64 Hz, H17′), 7.46 (m, 2H, H3′ + H11′), 7.37 (d, 1H, J = 8.2 Hz, H10′), 7.34 (m, 2H, H2(E)′ + H2(Z)′), 7.26 (d, 1H, J = 7.94 Hz, H4′), 7.09 (d, 2H, J = 8.72 Hz, H12d + H16d), 6.03 (t, 1H, J = 5.74 Hz, H2d or H4d), 5.95 (t, 1H, J = 5.73 Hz, H2d or H4d), 5.90 (d, 1H, J = 6.05 Hz, H1d or H5d), 5.84 (d, 1H, J = 18.4 Hz, H14′), 5.83 (t, 1H, J = 5.59 Hz, H3d), 5.77 (d, 1H, J = 5.88 Hz, H1d or H5d), 5.22 (d, 1H, J = 17.07 Hz, H14′), 4.77 (d, 1H, J = 13.21 Hz, H7′), 4.64 (s, 2H, H10d), 4.09 (d, 2H, J = 6.09 Hz, H7d), 3.47 (d, 1H, J = 15.25 Hz, H7′). 1H NMR (500.32 MHz, DMSO- d6): Z isomer, δ 11.85 (s, 1H, H12′), 9.88 (s, 1H, H17d), 9.67 (s, 1H, H5′), 9.03 (d, 1H, J = 5.39 Hz, H18′), 8.89 (t, 1H, J = 5.93 Hz, H8d), 8.32 (d, 1H, J = 1.69 Hz, H8′), 7.96 (t, 1H, J = 7.65 Hz, H16′), 7.87 (d, 2H, J = 8.72 Hz, H13d + H15d), 7.81 (d, 1H, J = 7.76 Hz, H1′), 7.72 (d, 1H, J = 8.26 Hz, H4′), 7.51 (m, 2H, H3′ + H17′), 7.41 (m, 2H, H11′ + H15′), 7.34 (m, 2H, H2(E)′ + H2(Z)′), 7.22 (dd, 1H, J = 1.8 and 8.52 Hz, H10′), 7.15 (d, 2H, J = 8.69 Hz, H12d + H16d), 6.27 (t, 1H, J = 5.79 Hz, H2d or H4d), 6.14 (t, 1H, J = 5.66 Hz, H2d or H4d), 6.06 (d, 1H, J = 5.84 Hz, H1d or H5d), 5.98 (m, 2H, H3d + H1d or H5d), 5.16 (d, 1H, J = 18.15 Hz, H14′), 4.99 (d, 1H, J = 18.27 Hz, H14′), 4.92 (d, 1H, J = 13.99 Hz, H7′), 4.76 (s, 2H, H10d), 4.42 (ddd, 2H, J = 5.86, 14.81, and 47.62 Hz, H7d), 3.69 (d, 1H, J = 14.18 Hz, H7′). 13C NMR (125.81 MHz, DMSO-d6): E isomer, δ 191.82 (C17d), 168.16 (C9d), 167.64 (C6′), 162.75 (C11d), 161.52 (C14a′), 155.37 (C18′), 140.07 (C16′), 136.50 (C11a′), 135.78 (C4a′), 135.35 (C12a′), 132.17 (C13d + C15d), 130.67 (C14d), 129.39 (C3′), 128.66 (C7b′), 127.75 (C1′), 125.43 (C2′, C10′, or C17′), 125.34 (C2′, C10′, or C17′), 124.74 (C2′ or C10′), 122.31 (C4′), 122.19 (C12b′), 121.23 (C8′ or C15′), 121.18 (C8′ or C15′), 115.67(C12d + C16d), 114.18 (C11′), 112.61 (C9′), 107.21 (C7a′), 103.28 (C6d), 90.03 (C2d or C4d), 89.49 (C2d or C4d), 82.49 (C1d or C5d), 81.97 (C1d or C5d), 80.78 (C3d), 67.27 (C10d), 62.52 (C14′), 40.71 (C7d), 24.02 (C7′). 13C NMR (125.81 MHz, DMSO-d6): Z isomer, δ 191.82 (C17d), 168.36 (C9d), 165.62 (C6′), 162.87 (C11d), 160.54 (C14a′), 155.24 (C18′), 139.65 (C16′), 136.44 (C11a′), 136.13 (C4a′), 133.89 (C12a′), 132.17 (C13d + C15d), 130.67 (C14d), 128.75 (C7b′), 128.48 (C3′), 127.55 (C1′), 125.15 (C2′, C10′, or C17′), 124.98 (C2′, C10′, or C17′), 124.85 (C2′, C10′, or C17′), 123.57 (C4′), 123.08 (C8′), 122.56 (C12b′), 121.12 (C15′), 115.73 (C12d + C16d), 113.37 (C11′), 111.69 (C9′), 109.13 (C7a′), 102.16 (C6d), 88.96 (C2d or C4d), 88.29 (C2d or C4d), 83.19 (C1d or C5d), 82.28 (C1d, C5d, or C3d), 81.74 (C1d, C5d, or C3d), 67.41 (C10d), 62.68 (C14′), 40.71 (C7d), 32.77 (C7′). 15N NMR (50.70 MHz, DMSO-d6): E isomer, δ 109.42 (N12′), 107.95 (N5′), 88.39 (N8d). 15N NMR (50.70 MHz, DMSO-d6): Z isomer, δ 107.95 (N12′), 107.46 (N5′), 88.39 (N8d). b. NMR Characterization of E/Z Isomers in MeOH-d4. 1H NMR (500.32 MHz, MeOH-d4): E isomer, δ 9.87 (s, 1H, H17d), 9.42 (s, 1H, H5′), 9.08 (d, 1H, J = 5.13 Hz, H18′), 8.11 (d, 1H, J = 1.72 Hz, H8′), 8.06 (t, 1H, J = 7.76 Hz, H16′), 7.88 (d, 2H, J = 8.81 Hz, H13d + H15d), 7.84 (dd, 1H, J = 1.46 and 7.58 Hz), 7.70 (d, 1H, J = 7.79 Hz, H15′), 7.54 (t, 1H, J = 6.66 Hz, H17′), 7.45−7.33 (m, 3H), 7.29 (m, 2H, H4′ + 1H), 7.12 (d, 2H, J = 8.76 Hz, H12d + H16d), 5.94 (t, 1H, J = 5.81 Hz, H2d, H3d, or H4d), 5.78 (d, 1H, J = 17.1 Hz, H14′), 5.75−5.72 (m (d + t), 2H), 5.66 (t, 1H, J = 5.67 Hz, H2d, H3d, or H4d), 5.56 (d, 1H, J = 5.88 Hz, H1d or H5d), 5.29 (d, 1H, J = 17.01 Hz, H14′), 4.90 (d, 1H, J = 15.08 Hz, H7′), 4.64 (d, 2H, J = 2.99 Hz, H10d), 4.13 (dd, 2H, J = 13.07 and 50.57 Hz, H7d), 3.29 (d, 1H, J = 14.81 Hz, H7′) [based only on the 1H,1H ROESY NMR plot and due to absence of NH signals (except H5), protons H1, H2, H3, H10, and H11 (5H) were not assigned]. 1H NMR (500.32 MHz, MeOH-d4): Z isomer, δ 9.84 (s, 1H, H17d), 8.99 (d, 1H, J = 5.24 Hz, H18′), 8.35 (d, 1H, J = 1.73 Hz, H8′), 7.92 (t, 1H, J = 7.68 Hz), 7.85 (d, 2H, J = 8.78 Hz, H13d + H15d), 7.79 (dd, 1H, J = 1.44 and 7.82 Hz), 7.61 (d, 1H, J = 8.11 Hz), 7.49 (t, 1H, J = 6.95 Hz), 7.45−7.33 (m, 4H, H15′ + H17′ + 2H), 7.23 (dd, 1H, J = 1.86 and 8.6 Hz), 7.18 (d, 2H, J = 8.74 Hz, H12d + H16d), 6.21 (t, 1H, J = 5.75 Hz, H2d, H3d, or H4d), 6.05 (t, 1H, J = 5.68 Hz, H2d, H3d, or H4d), 6.03 (d, 1H, J = 5.99 Hz, H1d or H5d), 5.92 (d, 1H, J = 6.13 Hz, H1d or H5d), 5.89 (t, 1H, J = 5.55 Hz, H2d, H3d, or H4d), 5.11 (d, 1H, J = 18.09 Hz, H14′), 4.97 (d, 1H, J = 14.08 Hz, H7′), 4.92 (d, 1H, J = 17.77 Hz, H14′), 4.82 (m, 2H, H10d), 4.59 (m, 2H, H7d), 3.69 (d, 1H, J = 13.95 Hz, H7′) [based only on the 1H,1H ROESY NMR plot and due to the absence of NH signals, protons H1, H2, H3, H4, H10, H11, and H16 (7H) were not assigned]. 12672 dx.doi.org/10.1021/ic201801e| Inorg. Chem. 2011, 50, 12669−12679