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Dalton Transactions
Page 12 of 15
ARTICLE
Journal Name
ESI-MS (MeOH): m/z = 638.1 ([M-PF6]). Elemental analysis (% 6.8 Hz, H27’), 0.91 (m, 3H, H28). 13C-NMR (151 MHz, acetone-d6,
DOI: 10.1039/C6DT04729G
found): C, 46.07; H, 3.52; N, 12.49. Calcd for C30H27ClF6N7OPRu: C, 298K) δ 204.97 (C6), 161.42 (C20), 160.02 (C34), 158.07 (C14),
46.01; H, 3.48; N, 12.52.
151.65 (C24), 150.15 (C13), 149.42 (C30), 136.55 (C32), 125.73
[RuII(Me-L2)(tpm)Cl]PF6 (3(PF6)): [Ru(tpm)Cl3] (130 mg, 0.3 mmol), (C22), 133.74 (C10), 131.47 (C11), 125.00 (C3), 124.30 (C12), 123.63
1,4-bis (1-methylimidazolium-1-yl)phthalazine dichloride (H2L1(Cl)2) (C21), 123.13 (C33), 121.52 (C8), 121.01 (C23), 120.70 (C9), 120.64
(73 mg, 0.2 mmol) and LiCl (38 mg 0.9 mmol) were mixed in a round (C31), 119.44 (C7), 118.85 (C4), 67.49 (C25), 66.09 (C29), 61.96
bottom flask and dry methanol (20 mL) was added as solvent. (C27), 53.89 (C18), 35.45 (C1), 7.98 (C28). UV/vis (methanol): λmax
,
Triethylamine (121 mg, 166 μL, 1.2 mmol) was added to the nm (ε, M-1·cm-1)= 299 (5226), 434 (5612). ESI-MS (MeOH): m/z =
solution and the mixture was refluxed at 65°C for 16 hours. After 604.1 ([M-PF6]). Elemental analysis (% found): C, 43.37; H, 3.94; N,
cooling to room temperature, the reaction crude was filtered 13.05. Calcd for C27H29ClF6N7OPRu: C, 43.29; H, 3.90; N, 13.09.
through celite® to remove the black solid formed and 20 drops of cis-[RuII(Me-L2)(trpy)(OH2)](PF6)2 (2a(PF6)2): 1a+ (120 mg, 0.16
saturated aqueous NH4PF6 were added to the filtrate. The mmol) was dissolved in a mixture of acetone and water (acetone:
methanolic solution was concentrated in a rotary evaporator until water = 1: 3, 40 mL). AgBF4 (109 mg, 0.56 mmol) was added into the
about 10 mL and a brown precipitate was obtained. The precipitate solution, which was then refluxed at 90°C for 4 hours. After cooling
was filtered off, washed with diethyl ether and dried under vacuum. to room temperature, the reaction crude was filtered through
Yield: 88 mg (60%). 1H-NMR (600 MHz, acetone-d6, 298K) δ 9.66 (s, celite® to remove the black solid formed. The red-brown solution
1H, H24), 8.88 (d, 1H, J4-3 = 2.3 Hz, H4), 8.87 (d, 1H, J9-10 = 8.6 Hz, was concentrated under vacuum until about 20 mL left, followed by
H9), 8.68 (d, 1H, J20-21 = 1.6 Hz, H20), 8.57 (d, 1H, J31-32 = 2.3 Hz, centrifugation (10000rpm, 10min) to remove the potential colloidal
H31), 8.52 (d, 1H, J22-21 = 2.2 Hz, H22), 8.47 (d, 1H, J33-32 = 1.7 Hz, silver still remaining. To the clear red solution 20 drops of saturated
H33), 8.46 (d, 1H, J26-27 = 2.5 Hz, H26), 8.39 (d, 1H, J12-11 = 8.0 Hz, aqueous NH4PF6 solution were added and the precipitate formed
H12), 8.20 (t, 1H, J10-9,11 = 7.3 Hz, H10), 8.07 (t, 1H, J11-10,12 = 7.6 Hz, was filtered off, washed with diethylether and dried under vacuum.
H11), 7.64 (d, 1H, J3-4 = 2.3 Hz, H3), 6.89 (d, 1H, J28-27 = 1.9 Hz, H28), Yield: 91 mg (65%). 1H-NMR (600 MHz, acetone-d6, 298K) δ 9.01 (d,
6.74 (t, 1H, J21-20,22 = 2.3 Hz, H21), 6.67 (t, 1H, J32-31,33 = 2.4 Hz, H32), 1H, J4-3 = 2.4 Hz, H4), 8.80 (d, 2H, J26-27 = 7.4 Hz, H26), 8.78 (d, J9-10
6.33 (t, 1H, J27-26,28 = 2.4 Hz, H27), 4.16 (s, 3H, H18), 3.73 (s, 3H, H1). 8.7 Hz, H9), 8.62 (d, 2H, J23-22 = 8.0 Hz, H23), 8.44 (t, 2H, J27-26,26’
13C-NMR (151 MHz, acetone-d6, 298K) δ 205.44 (C6), 157.87 (C14), 8.1 Hz, H27), 8.19 (d, 2H, J20-21 = 5.0 Hz, H20), 8.12 (t, 1H, J10-9,11
151.40 (C7), 149.12 (C33), 146.71 (C28), 146.66 (C20), 134.70 (C26), 8.7 Hz, H10), 8.04-8.00 (m, 4H, H12, H3, H22), 7.91 (t, 1H, J11-10,12
=
=
=
=
133.97 (C31), 133.75 (C10), 132.43 (C22), 132.27 (C11), 124.89 (C3), 7.5 Hz, H11), 7.37 (m, 2H, H21), 4.56 (s, 3H, H1), 3.46 (s, 3H, H18).
124.34 (C12), 121.57 (C8), 121.28 (C9), 120.17 (C13), 119.63 (C4), 13C-NMR (151 MHz, acetone-d6, 298K) δ 200.62 (C6), 159.47 (C24),
108.41 (C32), 108.27 (C27), 107.51 (C21), 76.77 (C24), 55.04 (C18), 158.01 (C14), 157.82 (C20), 156.41 (C25), 153.08 (C7), 138.22 (C22),
36.27 (C1). UV/vis (methanol): λmax, nm (ε, M-1·cm-1)= 302 (7799), 137.65 (C27), 134.20 (C10), 132.83 (C11), 127.53 (C21), 126.29 (C3),
410 (4745). ESI-MS (MeOH): m/z = 591.1 ([M-PF6]). Elemental 124.05 (C12), 123.85 (C23), 122.38 (C26), 121.12 (C9), 120.90 (C8),
analysis (% found): C, 37.60; H, 3.05; N, 18.99. Calcd for 119.57 (C14), 119.21 (C3), 54.43 (C18), 36.55 (C1). UV/vis
C23H22ClF6N10OPRu: C, 37.53; H, 3.01; N, 19.03.
(methanol): λmax, nm (ε, M-1·cm-1)= 275 (12189), 309 (13040), 388
trans,fac-[RuII(Me-L2)(bpea)Cl]PF6 (5(PF6)): [Ru(bpea)Cl3] (130 mg, (4338), 467 (4474). ESI-MS (MeOH): m/z = 594.1 ([M-2PF6+1]).
0.3 mmol), 1,4-bis(1-methylimidazolium-1-yl)phthalazine dichloride Elemental analysis (% found): C, 38.14; H, 2.89; N, 11.06. Calcd for
(H2L1(Cl)2) (73 mg, 0.2 mmol) and LiCl (38 mg 0.9 mmol) were mixed C28H25F12N7O2P2Ru: C, 38.11; H, 2.86; N, 11.11.
in a round bottom flask and dry methanol (20 mL) was added as cis-[RuII(iPr-L2)(trpy)(OH2)](PF6)2 (2b(PF6)2): 1b+ (120mg, 0.15 mmol)
solvent. Triethylamine (121 mg, 166 μL, 1.2 mmol) was added to the was dissolved in a 40 mL mixture of acetone and water (1:3). AgBF4
solution and the mixture was refluxed at 65°C for 16 hours. After (109 mg, 0.56 mmol) was then added to the solution, which was
cooling to room temperature, the reaction crude was filtered then refluxed at 90°C for 4 hours. After cooling to room
through celite® to remove the black solid formed and 20 drops of temperature, the reaction crude was filtered through celite® to
saturated aqueous NH4PF6 were added to the filtrate. The remove the silver chloride formed. The brown filtrate was then
methanolic solution was concentrated in a rotary evaporator until concentrated in a rotary evaporator until about 20 mL, followed by
about 10 mL left and a brown precipitate appeared. The precipitate centrifugation (10000 rpm, 10 min) to remove the remaining solids.
was filtered, washed with diethyl ether and dried under vacuum. To the clear red solution 20 drops of a saturated aqueous NH4PF6
Yield: 68 mg (45%). 1H-NMR (600 MHz, acetone-d6, 298K) δ 9.63 (d, solution were added. The brown precipitate formed was filtered off,
1H, J20-21 = 5.3 Hz, H20), 9.56 (d, 1H, J34-33 = 5.0 Hz, H34), 8.84 (d, 1H, washed with diethyl ether and dried under vacuum. Yield: 91 mg
J4-3 = 2.0 Hz, H4), 8.79 (d, 1H, J9-10 = 8.3 Hz, H9), 8.25 (d, 1H, J12-11
8.0 Hz, H12), 8.12 (t, 1H, J10-9,11 = 7.5 Hz, H10), 7.97 (t, 1H, J11-10,12
7.6 Hz, H11), 7.92 (t, 1H, J32-31,33 = 7.3 Hz, H32), 7.82 (t, 1H, J22-21,23
=
=
=
(65%). 1H-NMR (600 MHz, acetone-d6, 298K) δ 9.03 (d, 1H, J4-3 = 2.4
Hz, H4), 8.84 (d, 2H, J27-28 = 6.7 Hz, H27), 8.81 (d, 1H, J9-10 = 8.7 Hz,
H9), 8.63 (d, 2H, J24-23 = 8.0 Hz, H24), 8.50 (t, 1H, J28-27,27’ = 8.1 Hz,
7.4 Hz, H22), 7.58 (m, 2H, J3-4 = 2.3 Hz, J31-32 = 7.3 Hz, H3, H31), 7.50 H28), 8.23 (dd, 2H, J21-22,23 = 10.5, 5.6 Hz, H21), 8.13 (t, 1H, J10-9,11
(m, 1H, J23-22,33-32,34 = 7.3 Hz, H23, H33), 7.41 (t, 1H, J21-20,22 = 6.5 Hz, 8.5, Hz, H10), 8.10 (d, 1H, J12-11 = 8.7 Hz, H12), 8.06-8.01 (m, 3H, H3,
H21), 4.52-4.42 (m, 4H, H25, H29) 3.65 (s, 3H, H18), 3.58 (s, 3H, H1), H23), 7.93 (t, 1H, J11-10,12 = 7.6 Hz, H11), 7.38 (ddd, 1H, J22-21,23,24
2.53 (m, 1H, J27-27’,28 = 13.8, 6.8 Hz, H27), 2.35 (m, 1H, J27’-27,28 = 13.7, 7.0, 5.6, 1.2 Hz, H22), 4.58 (s, 3H, H1), 4.49 (dt, 1H, J18-19,19’ = 12.3,
=
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12 | Dalton Trans., 2016, 00, 1-3
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