Dalton Transactions
Paper
[Ru(η6-p-cymene)Br2]2 (220 mg, 0.28 mmol) affording 5 as a red
[Chlorido{3-(oxo-κO)-2-phenyl-chromen-4(1H)-onato-κO}-
powder (210 mg, 64%). Mp: 164–167 °C (decomp.); 1H NMR (η6-toluene)ruthenium(II)] (8). The reaction was performed
(500.10 MHz, CDCl3): δ = 1.43–1.45 (m, 6H, CH3,Cym), 2.43 (s, according to the general complexation procedure using a
3H, CH3,Cym), 3.00–3.07 (m, 1H, CHCym), 5.41 (dd, 4J(H,H) = (180 mg, 0.76 mmol), NaOMe (45 mg, 0.84 mmol) and [Ru(η6-
3
3
1 Hz, J(H,H) = 8 Hz, 2H, H3/H5Cym), 5.68 (dd, J(H,H) = 5 Hz, toluene)Cl2]2 (200 mg, 0.38 mmol) affording 8 as an orange
3J(H,H) = 5 Hz, 2H, H2/H6Cym), 7.33–7.36 (m, 1H, H7), 7.44 (d, powder (148 mg, 42%). Mp: 218–220 °C (decomp.); 1H NMR
3J(H,H) = 9 Hz, 2H, H3′/H5′), 7.54 (d, J(H,H) = 8 Hz, 1H, H8), (500.10 MHz, CDCl3): δ = 2.41 (s, 3H, CH3,Tol), 5.39 (dd, J(H,
3
3
7.60–7.64 (m, 1H, H6), 8.21 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz, H) = 5 Hz, J(H,H) = 5 Hz, 2H, H2/H6Tol), 5.61 (dd, J(H,H) =
3
3
1H, H5), 8.55 (d, 3J(H,H) = 9 Hz, 2H, H2′/H6′) ppm; 13C{1H} 5 Hz, J(H,H) = 5 Hz, 1H, H1Tol), 5.88–5.90 (m, 2H, H3/H5Tol),
3
NMR (125.75 MHz, CDCl3): δ = 19.1 (CH3,Cym), 22.5 (CH3,Cym), 7.34–7.36 (m, 1H, H7), 7.39–7.42 (m, 1H, H4′), 7.48–7.51 (m,
31.3 (CHCym), 78.4 (C3/C5Cym), 81.0 (C2/C6Cym), 95.9 (C4Cym), 2H, H3′/H5′), 7.57 (d, 3J(H,H) = 8 Hz, 1H, H8), 7.61–7.64 (m, 1H,
99.3 (C1Cym), 117.8 (C8), 120.0 (C8a), 124.2 (C7), 124.7 (C5), H6), 8.24 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz, 1H, H5), 8.61 (dd,
128.4 (C2′/C6′), 128.5 (C3′/C5′), 131.0 (C4′), 132.8 (C6), 134.9 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz, 2H, H2′/H6′) ppm; 13C{1H}
(C2), 147.9 (C1′), 153.8 (C4a), 154.8 (C3), 183.7 (C4) ppm; NMR (125.75 MHz, CDCl3): δ = 19.1 (CH3,Tol), 29.9 (CHTol),
elemental analysis calcd for C25H22ClBrO3Ru·0.25H2O: C 50.77, 75.1 (C1Tol), 76.7 (C2/C6Tol), 85.2 (C3/C5Tol), 98.9 (C4Tol), 117.8
H 3.83%; found: C 50.79, H 3.77%.
(C8), 119.9 (C8a), 124.2 (C7), 124.6 (C5), 127.4 (C2′/C6′), 128.3
[Iodido{3-(oxo-κO)-2-phenyl-chromen-4(1H)-onato-κO}- (C3′/C5′), 129.4 (C4′), 132.3 (C2), 132.7 (C6), 149.4 (C1′), 153.9
(η6-p-cymene)ruthenium(II)] (6). The reaction was performed (C4a), 154.6 (C3), 183.4 (C4) ppm; elemental analysis calcd for
according to the general complexation procedure using a (128 mg, C22H17ClO3Ru·0.5H2O: C 55.64, H 3.82%; found: C 55.87,
0.54 mmol), NaOMe (33 mg, 0.61 mmol) and [Ru(η6-p-cymene)I2]2 H 3.72%.
(208 mg, 0.21 mmol) affording 6 as red crystals (177 mg, 70%).
[Chlorido{3-(oxo-κO)-2-(4-chlorophenyl)-chromen-4(1H)-
1
Mp: 131–134 °C (decomp.); H NMR (500.10 MHz, CDCl3): δ = onato-κO}(η6-toluene)ruthenium(II)] (9). The reaction was per-
1.47–1.48 (m, 6H, CH3,Cym), 2.45 (s, 3H, CH3,Cym), 3.05–3.12 formed according to the general complexation procedure
3
3
(m, 1H, CHCym), 5.45 (dd, J(H,H) = 5 Hz, J(H,H) = 5 Hz, 2H, using c (206 mg, 0.76 mmol), NaOMe (45 mg, 0.84 mmol) and
H3/H5Cym), 5.73 (dd, 3J(H,H) = 5 Hz, 3J(H,H) = 5 Hz, 2H, [Ru(η6-p-cymene)Cl2]2 (200 mg, 0.38 mmol) affording 9 as red
H2/H6Cym), 7.34–7.37 (m, 1H, H7), 7.39–7.42 (m, 1H, H4′), crystals (281 mg, 74%). Mp: 217–219 °C (decomp.); 1H NMR
7.47–7.50 (m, 2H, H3′/H5′), 7.58 (d, 3J(H,H) = 8 Hz, 1H, H8), (500.10 MHz, CDCl3): δ = 2.40 (s, 3H, CH3,Tol), 5.39 (dd, 3J(H,H) =
3
3
7.61–7.64 (m, 1H, H6), 8.20 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz, 5 Hz, J(H,H) = 5 Hz, 2H, H2/H6Tol), 5.61 (dd, J(H,H) = 5 Hz,
1H, H5), 8.61 (dd, J(H,H) = 1 Hz, J(H,H) = 8 Hz, 2H, H2′/H6′) 3J(H,H) = 5 Hz, 1H, H1Tol), 5.88–5.91 (m, 2H, H3/H5Tol),
ppm; 13C{1H} NMR (125.75 MHz, CDCl3): δ = 18.6 (CH3,Cym), 7.34–7.38 (m, 1H, H7), 7.50 (d, 3J(H,H) = 8 Hz, 2H, H3′/H5′),
22.7 (CH3,Cym), 31.9 (CHCym), 77.7 (C3/C5Cym), 80.8 (C2/C6Cym), 7.52–7.54 (m, 1H, H4′), 7.56 (d, 3J(H,H) = 8 Hz, 1H, H8),
95.0 (C4Cym), 99.5 (C1Cym), 117.9 (C8), 120.1 (C8a), 124.1 (C7), 7.62–7.65 (m, 1H, H6), 8.24 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz,
124.6 (C5), 127.2 (C2′/C6′), 128.2 (C3′/C5′), 129.3 (C4′), 132.5 1H, H5), 8.56 (d, 3J(H,H) = 8 Hz, 2H, H2′/H6′) ppm; 13C{1H}
(C2), 132.6 (C6), 149.1 (C1′), 153.9 (C4a), 155.1 (C3), 183.7 (C4) NMR (125.75 MHz, CDCl3): δ = 19.1 (CH3,Tol), 29.9 (CHTol),
ppm; elemental analysis calcd for C25H23IO3Ru·0.25H2O: C 75.1 (C1Tol), 76.7 (C2/C6Tol), 85.2 (C3/C5Tol), 98.6 (C4Tol), 117.9
4
3
49.72, H 3.92%; found: C 49.61, H 3.68%.
(C8), 120.0 (C8a), 124.3 (C7), 124.7 (C5), 128.6 (C2′/C6′/C3′/
[Iodido{3-(oxo-κO)-2-(4-chlorophenyl)-chromen-4(1H)-onato-κO}- C5′), 130.8 (C2), 133.0 (C6), 135.1 (C4′), 148.2 (C1′), 153.9
(η6-p-cymene)ruthenium(II)] (7). The reaction was performed (C4a), 154.6 (C3), 183.6 (C4); elemental analysis calcd for
according to the general complexation procedure using c C22H16Cl2O3Ru: C 52.81, H 3.22%; found: C 52.62, H 3.14%.
(151 mg, 0.55 mmol), NaOMe (36 mg, 0.67 mmol) and [Ru(η6-
[Chlorido{3-(oxo-κO)-2-phenyl-chromen-4(1H)-onato-κO}-
p-cymene)I2]2 (217 mg, 0.22 mmol) affording 7 as a deep red (η6-biphenyl)ruthenium(II)] (10). The reaction was performed
powder (190 mg, 68%). Mp: 93–95 °C (decomp.); 1H NMR according to the general complexation procedure using a
(500.10 MHz, CDCl3): δ = 1.45–1.46 (m, 6H, CH3,Cym), 2.42 (s, (170 mg, 0.71 mmol), NaOMe (43 mg, 0.80 mmol) and [Ru(η6-
3H, CH3,Cym), 3.03–3.09 (m, 1H, CHCym), 5.44 (dd, 3J(H,H) = biphenyl)Cl2]2 (200 mg, 0.31 mmol) affording 10 as a deep red
3
3
5 Hz, J(H,H) = 5 Hz, 2H, H3/H5Cym), 5.72 (dd, J(H,H) = 5 Hz, powder (279 mg, 86%). Mp: 203–206 °C (decomp.); 1H NMR
3J(H,H) = 5 Hz, 2H, H2/H6Cym), 7.33–7.36 (m, 1H, H7), 7.43 (d, (500.10 MHz, CDCl3):
δ = 5.91–5.93 (m, 1H, H1Biphen),
3J(H,H) = 9 Hz, 2H, H3′/H5′), 7.54 (d, J(H,H) = 8 Hz, 1H, H8), 5.96–5.97 (m, 2H, H2/H6Biphen), 6.01–6.04 (m, 2H, H3/H5Biphen),
3
7.60–7.63 (m, 1H, H6), 8.18 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz, 7.32–7.35 (m, 1H, H7), 7.39–7.44 (m, 3H, H3′/H5′, H10Biphen),
1H, H5), 8.54 (d, 3J(H,H) = 9 Hz, 2H, H2′/H6′) ppm; 13C{1H} 7.47–7.51 (m, 3H, H4′, H9/H11Biphen), 7.55 (d, J(H,H) = 8 Hz,
3
NMR (125.75 MHz, CDCl3): δ = 19.1 (CH3,Cym), 22.6 (CH3,Cym), 1H, H8), 7.60–7.63 (m, 1H, H6), 7.90 (dd, 4J(H,H) = 1 Hz,
31.5 (CHCym), 78.0 (C3/C5Cym), 80.9 (C2/C6Cym), 95.6 (C4Cym), 3J(H,H) = 8 Hz, 1H, H8/H12Biphen), 8.16 (dd, 4J(H,H) = 1 Hz,
99.3 (C1Cym), 117.9 (C8), 120.0 (C8a), 124.3 (C7), 124.6 (C5), 3J(H,H) = 8 Hz, 1H, H5), 8.47 (dd, 4J(H,H) = 1 Hz, 3J(H,H) = 8 Hz,
128.3 (C2′/C6′), 128.5 (C3′/C5′), 131.0 (C4′), 132.9 (C6), 134.9 2H, H2′/H6′) ppm; 13C{1H} NMR (125.75 MHz, CDCl3): δ =
(C2), 148.0 (C1′), 153.9 (C4a), 155.0 (C3), 183.8 (C4) ppm; 78.4 (C2/C6Biphen), 78.8 (C1Biphen), 83.0 (C3/C5Biphen), 96.9
elemental analysis calcd for C25H22ClIO3Ru·0.25H2O: C 47.03, (C4Biphen), 117.8 (C8), 120.0 (C8a), 124.2 (C7), 124.5 (C5), 127.4
H 3.55%; found: C 46.95, H 3.50%.
(C2′/C6′), 128.2 (C3′/C5′), 128.8 (C9/C11Biphen), 129.1 (C8/
This journal is © The Royal Society of Chemistry 2013
Dalton Trans., 2013, 42, 6193–6202 | 6199