Paper
Dalton Transactions
(s, 2H, –2OH), 9.00 (d, 2H, J = 8.0 Hz), 8.89 (d, 2H, J = 7.9 Hz), 0.2 mmol) instead of Δ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-D-tar-
7.73 (dd, 2H, J = 7.6 Hz), 6.70 (s, 2H), 6.23 (s, 1H).
trate]·12H2O. Yield: 0.098 g, 64.6%. The elemental analysis,
1H NMR, and mass spectral data of Λ-2 were observed to be
quite similar to its Δ enantiomer, within experimental error.
Synthesis of complexes
Δ-[Ru(bpy)2(2,4,6-PIPTH)](ClO4)2
[O,O′-dibenzoyl-D-tartrate]·12H2O and Λ-[Ru(bpy)2(py)2][O,O′- (153.1), 274 (−60.0), 239 (−17.3).
(Δ-1). Δ-[Ru(bpy)2(py)2]- CD [λ/nm (Δε/M−1 cm−1)] (H2O): 471 (12.2), 419 (−12.9), 291
dibenzoyl-L-tartrate]·12H2O were synthesized according to
Δ-[Ru(bpy)2(2,5-PIPDH)](ClO4)2 (Δ-3). A mixture of Δ-[Ru-
methods described in the literature.46 A mixture of Δ-[Ru(bpy)2- (bpy)2(py)2][O,O′-dibenzoyl-D-tartrate]·12H2O (0.2 g, 0.2 mmol),
(py)2][O,O′-dibenzoyl-D-tartrate]·12H2O (0.2 g, 0.2 mmol), 2,4,6- 2,5-PIPTH (0.066 g, 0.2 mmol) and ethylene glycol (10 mL) was
PIPTH (0.070 g, 0.2 mmol) and ethylene glycol (10 mL) was refluxed under argon for 8 h, and the color of the solution
refluxed under argon for 8 h, and the color of the solution changed from purple to red. The solution was cooled to room
changed from purple to red. The solution was cooled to room temperature, and 30 mL of H2O was added. After filtration, a
temperature, and 30 mL of H2O was added. After filtration, a dark red precipitate was obtained by the dropwise addition of
dark red precipitate was obtained by the dropwise addition of an aqueous NaClO4 solution. The product was recrystallized
an aqueous NaClO4 solution. The product was recrystallized from toluene–acetonitrile (1 : 1). Yield: 0.1 g, 67.0%. Anal.
from toluene–acetonitrile (1 : 1). Yield: 0.12 g, 79.2%. Anal. Calcd for C39H28N8O2Ru: C, 63.15; H, 3.80; N, 15.11; O, 4.31;
Calcd for C39H28N8O3Ru: C, 61.82; H, 3.72; N, 14.79; O, 6.33; Ru, 13.63. Found: C, 63.10; H, 3.85; N, 15.10; O, 4.41; Ru,
Ru, 13.34. Found: C, 61.85; H, 3.73; N, 14.74; O, 6.37; Ru, 13.42. ES-MS [CH3CN, m/z]: 742 ([M − 2ClO4 + H]+), 371
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13.31. ES-MS [CH3CN, m/z]: 758 ([M − 2ClO4 + H]+), H NMR ([M − 2ClO4]2+). H NMR (400 MHz, DMSO-d6): δ 9.52 (s, 1H),
(400 MHz, DMSO-d6): δ 9.28 (s, 3H), 8.82 (dd, 4H, J = 9.0 Hz), 9.32 (s, 1H), 9.09 (d, 1H, J = 8.2 Hz), 8.81 (dd, 3H, J = 8.0 Hz),
8.19 (t, 2H, J = 7.8 Hz), 8.08 (t, 4H, J = 7.8 Hz), 8.00 (dd, 2H, J = 8.20 (t, 2H, J = 7.8 Hz), 8.06 (dd, 4H, J = 7.4 Hz), 7.90 (dd, 2H,
5.5 Hz), 7.83 (td, 4H, J = 7.8 Hz), 7.57 (t, 2H, J = 6.7 Hz), 7.32 J = 7.8 Hz), 7.83 (d, 4H, J = 7.8 Hz), 7.57 (td, 2H, J = 8.1 Hz),
(t, 4H, J = 7.9 Hz), 6.03 (s, 2H). 379 ([M − 2ClO4]2+). CD [λ/nm 7.33 (t, 4H, J = 7.6 Hz), 6.93 (s, 1H). 6.58 (d, 2H, J = 7.7 Hz).
(Δε/M−1 cm−1)] (H2O): 471 (−10.6), 420 (9.7), 291 (−116.3), 275 CD [λ/nm (Δε/M−1 cm−1)] (H2O): 471 (−11.4), 420 (12.0), 291
(34.0), 240 (15.3).
(−144.9), 275 (53.0), 239 (14.8).
Λ-[Ru(bpy)2(2,4,6-PIPTH)](ClO4)2 (Λ-1). This complex was
Λ-[Ru(bpy)2(2,5-PIPDH)](ClO4)2 (Λ-3). This complex was syn-
synthesized in a manner identical to that described for Δ-1, thesized in a manner identical to that described for Δ-3,
with Λ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-L-tartrate]·12H2O (0.20 g, with Λ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-L-tartrate]·12H2O (0.20 g,
0.2 mmol) instead of Δ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-D-tartrate]· 0.2 mmol) instead of Δ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-D-tar-
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12H2O. Yield: 0.11 g, 72.8%. The elemental analysis, H NMR, trate]·12H2O. Yield: 0.11 g, 74.2%. The elemental analysis, H
and mass spectral data of Λ-1 were observed to be quite NMR, and mass spectral data of Λ-3 were observed to be
similar to its Δ enantiomer, within experimental error. CD quite similar to its Δ enantiomer, within experimental error.
[λ/nm (Δε/M−1 cm−1)] (H2O): 471 (10.3), 420 (−9.5), 291 (116.8), CD [λ/nm (Δε/M−1 cm−1)] (H2O): 471 (11.3), 420 (−12.0), 292
275 (−34.4), 240 (−15.2).
(144.8), 275 (−52.4), 240 (−14.4).
Δ-[Ru(bpy)2(2,3,4-PIPTH)](ClO4)2 (Δ-2). A mixture of Δ-[Ru-
Δ-[Ru(bpy)2(3,5-PIPDH)](ClO4)2 (Δ-4). A mixture of Δ-[Ru-
(bpy)2(py)2][O,O′-dibenzoyl-D-tartrate]·12H2O (0.2 g, 0.2 mmol), (bpy)2(py)2][O,O′-dibenzoyl-D-tartrate]·12H2O (0.2 g, 0.2 mmol),
2,3,4-PIPTH (0.070 g, 0.2 mmol) and ethylene glycol (10 mL) 3,5-PIPTH (0.066 g, 0.2 mmol) and ethylene glycol (10 mL) was
was refluxed under argon for 8 h, and the color of the solution refluxed under argon for 8 h, and the color of the solution
changed from purple to red. The solution was cooled to room changed from purple to red. The solution was cooled to room
temperature, and 30 mL of H2O was added. After filtration, a temperature, and 30 mL of H2O was added. After filtration, a
dark red precipitate was obtained by the dropwise addition of dark red precipitate was obtained by the dropwise addition of
an aqueous NaClO4 solution. The product was recrystallized an aqueous NaClO4 solution. The product was recrystallized
from toluene–acetonitrile (1 : 1). Yield: 0.1 g, 66.0%. Anal. from toluene–acetonitrile (1 : 1). Yield: 0.09 g, 60.8%. Anal.
Calcd for C39H28N8O3Ru: C, 61.82; H, 3.72; N, 14.79; O, 6.33; Calcd for C39H28N8O2Ru: C, 63.05; H, 3.85; N, 15.16; O, 4.38;
Ru, 13.34. Found: C, 61.80; H, 3.75; N, 14.70; O, 6.41; Ru, 13.56. Found: C, 63.75; H, 3.85; N, 15.10; O, 4.41;
Ru, 13.31. ES-MS [CH3CN, m/z]: 758 ([M − 2ClO4 + H]+), 379 Ru, 13.42. ES-MS [CH3CN, m/z]: 742 (M − 2ClO4 + H]+), 371
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([M − 2ClO4]2+). H NMR (400 MHz, DMSO-d6): δ 9.51 (s, 1H), ([M − 2ClO4]2+). H NMR (400 MHz, DMSO-d6): δ 9.26 (s, 2H),
9.49 (s, 1H), 9.34 (s, 1H), 9.08 (d, 1H, J = 8.2 Hz), 8.82 (dd, 3H, 8.84 (dd, 4H, J = 8.1 Hz), 8.17 (t, 2H, J = 7.9 Hz), 8.08 (t, 4H, J =
J = 8.0 Hz), 8.19 (t, 2H, J = 7.8 Hz), 8.09 (dd, 4H, J = 7.4 Hz), 8.2 Hz), 8.01 (d, 2H, J = 8.0 Hz), 7.84 (td, 4H, J = 7.8 Hz), 7.56
7.89 (dd, 2H, J = 7.8 Hz), 7.82 (d, 4H, J = 7.8 Hz), 7.58 (td, 2H, (t, 2H, J = 6.9 Hz), 7.33 (t, 4H, J = 8.0 Hz), 6.06 (s, 3H). CD
J = 8.1 Hz), 7.33 (t, 4H, J = 7.6 Hz), 6.58 (d, 1H, J = 6.9 Hz), 6.56 [λ/nm (Δε/M−1 cm−1)] (H2O): 471 (−10.4), 420 (11.4), 291
(d, 1H, J = 7.4 Hz). CD [λ/nm (Δε/M−1 cm−1)] (H2O): 471 (−150.4), 275 (52.7), 240 (12.8).
(−12.5), 420 (13.0), 291 (−153.7), 275 (59.9), 239 (17.7).
Λ-[Ru(bpy)2(3,5-PIPDH)](ClO4)2 (Λ-4). This complex was syn-
Λ-[Ru(bpy)2(2,3,4-PIPTH)](ClO4)2 (Λ-2). This complex was thesized in a manner identical to that described for Δ-4, with
synthesized in a manner identical to that described for Δ-2, Λ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-L-tartrate]·12H2O (0.20 g,
with Λ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-L-tartrate]·12H2O (0.20 g, 0.2 mmol) instead of Δ-[Ru(bpy)2(py)2][O,O′-dibenzoyl-D-
8914 | Dalton Trans., 2013, 42, 8907–8917
This journal is © The Royal Society of Chemistry 2013