Cyclometallated and Non-Cyclometallated Ruthenium(II) Complexes
FULL PAPER
(20 mL) was added to the filtrate. After decantation of the phases,
the benzene layer was washed with water and the combined aque-
ous layer was extracted with ether (3 ϫ 30 mL). The combined or-
ganic layers were evaporated and combined with the light yellow
solid. To this was added concentrated hydrochloric acid and the
mixture was heated to reflux for 2 h. On cooling, the mixture was
made basic with sodium carbonate, the organic layer was extracted
argon for 3 h. Yield 0.033 g (24%). Ϫ 1H NMR (200 MHz,
CD2Cl2): δ ϭ 8.56 (d, 2 H, J ϭ 8.22 Hz), 8.28 (s, 2 H), 8.25 (d, 2
H, J ϭ 8.22 Hz), 8.09 (td, 2 H, J ϭ 6.21 Hz, J ϭ 1.47 Hz), 7.82 (d,
2 H, J ϭ 8.21 Hz), 7.78 (d, 2 H, J ϭ 5.49 Hz), 7.70 (d, 2 H, J ϭ
8.24 Hz), 7.52Ϫ7.39 (m, 4 H), 7.02 (br, 2 H), 6.65Ϫ6.61 (m, 7 H),
5.96 (br, 3 H), 2.16 (s, 6 H). Ϫ MS (FAB-MS) (nitrobenzyl alcohol
Ϫ
matrix); m/z (%): 919 (20) [M Ϫ PF6Ϫ], 774 (10) [M Ϫ 2PF6
ϩ
Ϫ
with ether (2 ϫ 40 mL) and dried over sodium sulfate. Removal of eϪ], 617 (12) [M Ϫ 2PF6 Ϫ bipy ϩ eϪ].
the ether and purification on silica (dichloromethane/hexane 80:20)
gave 1.23 g (75%) of 3-acetyl-isoquinoline. Ϫ H NMR (200 MHz,
CDCl3): δ ϭ 9.26 (s, 1 H), 8.45 (s, 1 H), 8.05Ϫ7.94 (m, 2 H),
7.79Ϫ7.67 (m, 2 H), 2.80 (s, 3 H). Ϫ MS (EI); m/z: 171.
Ru(bipy)2(mapH)(PF6)2 (2): A suspension of Ru(bp)2Cl2·2H2O
(0.050 g, 0.096 mmol) and mapH (0.026 g, 0.09 mmol) in acetic
acid (7 mL) with 2Ϫ3 drops of N-ethylmorpholine was refluxed
1
1
under argon for 4 h. Yield 0.065 g (68%). Ϫ H NMR (200 MHz,
2,6-Diisoquinolyl-(4-tolyl)pyridine (dqpy): To a dried sample of 3-
CD2Cl2): δ ϭ 8.62 (d, 1 H, J ϭ 8.4 Hz), 8.56 (dd, 1 H, J ϭ 8.4 Hz,
acetyl-isoquinoline (1.23 g, 7.19 mmol), ammonium acetate (3.6 g, J ϭ 1.29 Hz), 8.40 (d, 1 H, J ϭ 7.86 Hz), 8.34 (d, 1 H, J ϭ 7.50 Hz),
46.7 mmol) and acetamide (5.54 g, 93.8 mmol) was added p-tolual- 8.31Ϫ8.22 (m, 4 H), 8.07 (td, 1 H, J ϭ 7.86 Hz, J ϭ 8.01 Hz),
dehyde (0.37 g, 3.11 mmol). The mixture was heated with stirring 7.99Ϫ7.94 (m, 4 H), 7.91 (d, 1 H, J ϭ 5.49 Hz), 7.74Ϫ7.62 (m, 4
to 170°C under solvent-free conditions under an atmosphere of
H), 7.49Ϫ7.31 (m, 6 H), 7.29 (br, 1 H), 7.07 (d, 1 H, J ϭ 5.67 Hz),
6.93 (t, 1 H, J ϭ 7.11 Hz), 3.70 (s, 3 H). Ϫ MS (FAB-MS) (nitro-
argon for 3 h. After this time the temperature of the reaction mix-
ture was lowered to 120°C and the mixture was added to a solution benzyl alcohol matrix); m/z (%): 845 (50) [M Ϫ PF6Ϫ], 700 (35) [M
Ϫ
of sodium hydroxide (2.8 g, 0.07 mol) in water (10 mL), a process
that resulted in a brownish oil. The mixture was left at this tem-
perature for a further 2 h. The dark brown oil and the yellow hot
solution was poured into a beaker and, after cooling, the brown
oil solidified. The solid was dissolved in acetic acid (10 mL) and
refluxed for 2 h. 47% hydrobromic acid (10 mL) was then added
and the mixture was left to stir at room temperture for a further
2 h. After this time, addition of a 5 solution of potassium hydrox-
ide (20 mL) resulted in the formation of a precipitate. The organic
layer was extracted with dichloromethane (3 ϫ 60 mL) and the
combined organic layers were washed with sodium hydrogen car-
bonate and dried over magnesium sulfate. After column chroma-
tography on alumina (hexane/ether; 8:2), dqpy was obtained as a
Ϫ 2PF6 ϩ eϪ].
Ru(mappy)2(PF6)2 (3): A suspension of Ru(mappy)Cl3 (0.060 g,
0.10 mmol) and mappy (0.039 g, 0.10 mmol) was heated to reflux
for 3 h in glacial acetic acid (6 mL) with 2Ϫ3 drops of N-ethyl-
1
morpholine. Yield 0.10 g (87%). Ϫ H NMR (200 MHz, CD2Cl2):
δ ϭ 8.77 (d, 2 H, J ϭ 8.6 Hz), 8.63 (d, 2 H, J ϭ 8.6 Hz), 8.44 (t,
4 H, J ϭ 8.06 Hz), 8.24 (s, 4 H), 7.69 (dd, 2 H, J ϭ 8.20 Hz, J ϭ
1.2 Hz), 7.36 (d, 2 H, J ϭ 8.34 Hz), 6.23Ϫ6.19 (br, 2 H), 6.15 (s, 2
H), 5.93Ϫ5.63 (m, 6 H), 3.76 (s, 6 H), 1.89 (s, 6 H). Ϫ MS (FAB-
MS) (nitrobenzyl alcohol matrix); m/z (%): 1001 (15) [M Ϫ PF6Ϫ],
Ϫ
856 (24) [M Ϫ 2PF6 ϩ eϪ].
Ru(ttpy)(mapH)(Cl)(PF6) (4) and Ru(ttpy)(map)(PF6) (7):
Ru(ttpy)Cl3 (0.10 g, 0.19 mmol) and mapH (0.054 g, 0.19 mmol)
were heated to reflux for 3 h in glacial acetic acid (6 mL) with 2Ϫ3
drops of N-ethylmorpholine. Yield: 0.042 g (35%) of the cyclomet-
allated product [Ru(ttpy)(map)PF6] (7) and 0.060 g (31%) of the
noncyclometallated product [Ru(ttpy)(mapH)(Cl)PF6] (4). Non-
cyclometallated complex (4): 1H NMR (200 MHz, CD3CN): δ ϭ
8.88 (s, 2 H), 8.54 (d, 2 H, J ϭ 7.78 Hz), 8.49 (d, 1 H, J ϭ 8.86 Hz),
8.32 (dd, 1 H, J ϭ 8.19 Hz), 8.22 (d, 1 H, J ϭ 8.23 Hz), 8.08 (d, 2
H, J ϭ 8.34 Hz), 7.85 (d, 1 H, J ϭ 8.88 Hz), 7.93Ϫ7.86 (m, 2 H),
7.77 (d, 1 H, J ϭ 1.62 Hz), 7.74 (d, 1 H, J ϭ 1.62 Hz), 7.69 (d, 1
H, J ϭ 1.65 Hz), 7.52 (d, 2 H, J ϭ 8.06 Hz), 7.34Ϫ7.25 (m, 3 H),
6.92 (td, 2 H, J ϭ 7.24 and 1.34 Hz ), 6.36 (dd, 1 H, J ϭ 5.92 Hz),
5.34 (d, 1 H, J ϭ 2.42 Hz), 3.39 (s, 3 H), 2.50 (s, 3 H). Ϫ MS;
1
white material (1.3 g, 43%). Ϫ H NMR (300 MHz, CDCl3): δ ϭ
9.36 (s, 2 H), 9.08 (s, 2 H), 8.83 (s, 2 H), 8.08 (d, 2 H, J ϭ 7.29 Hz),
8.03 (d, 2 H, J ϭ 8.04 Hz), 7.87 (d, 2 H, J ϭ 8.22 Hz), 7.74 (td, 2
H, J ϭ 1.28 Hz), 7.63 (td, 2 H, J ϭ 1.10 Hz), 7.33 (d, 2 H, J ϭ
7.86 Hz), 2.43 (s, 3 H). Ϫ MS (EI); m/z: 423.2.
Ru(mappy)Cl3: To absolute ethanol (30 mL) in a 100 mL round-
bottomed flask was added RuCl3·3H2O (0.042 g, 0.132 mmol) and
mappy (0.050 g, 0.132 mmol). The mixture was heated at reflux for
3 h with vigorous stirring. After this time, the reaction mixture was
cooled to room temperature and the fine brown powder was col-
lected by vacuum filtration, washed with cold absolute ethanol
(3 ϫ 30 mL) followed by Et2O (3 ϫ 30 mL) and dried under vac-
uum to give 0.065 g (84%) of Ru(mappy)Cl3.
Ϫ
m/z (%): 891 (35) [M Ϫ PF6Ϫ], 746 (100) [M Ϫ 2PF6 ϩ eϪ].
Ru(dqpy)Cl3: This compound was prepared in the same manner as
for the analogous compound, Ru(mappy)Cl3, in almost quantitat-
ive yield. The insoluble brown-red product obtained was used with-
out further purification.
Compound 7: 1H NMR (200 MHz, CD2Cl2): δ ϭ 8.75 (dd, 1 H,
J ϭ 6.72 Hz, J ϭ 1.56 Hz), 8.32 (d, 1 H, J ϭ 8.86 Hz), 8.34Ϫ8.17
(m, 5 H), 8.10 (s, 2 H), 7.87 (dd, 2 H, J ϭ 7.8 Hz, J ϭ 1.45 Hz),
7.79 (d, 2 H, J ϭ 8.32 Hz), 7.47 (d, 2 H, J ϭ 8.06 Hz), 7.37 (dd, 2
H, J ϭ 5.38 Hz, J ϭ 1.36 Hz), 7.17 (d, 2 H, J ϭ 8.34 Hz),
7.11Ϫ7.09 (m, 2 H), 6.45 (d, 2 H, J ϭ 8.88 Hz), 6.07 (d, 2 H, J ϭ
8.60 Hz), 3.52 (s, 3 H), 2.52 (s, 3 H). Ϫ MS (FAB-MS) (nitrobenzyl
General Workup Procedure for the Complexes 1 to 10: After reac-
tion, the solvent was removed under reduced pressure and the col-
ored solid was redissolved in methanol. The colored solution was
filtered to remove any trace of unchanged starting complex and the alcohol matrix); m/z (%): 855 (40) [Mϩ], 710 (100) [M Ϫ PF6Ϫ].
filtrate obtained was added to an aqueous solution of KPF6 (0.5 g
Ru(dqpy)2(PF6)2 (5):
0.11 mmol) and dqpy (0.049 g, 0.12 mmol) was heated to reflux for
6 h in glacial acetic acid (8 mL) with 2Ϫ3 drops of N-ethylmorph-
oline. Yield 0.040 g (30%). Ϫ H NMR (200 MHz, CD2Cl2): δ ϭ
A suspension of Ru(dqpy)Cl3 (0.070 g,
in 50 mL of water) to give a solid. This solid was purified by silica
gel chromatography, eluting with a mixture of CH2Cl2/CH3OH
(95:5) for all the complexes excepted for 5, where the elution was
1
performed with
(100:10:1).
a
CH3CN/H2O/saturated KNO3 mixture
9.09 (d, 8 H, J ϭ 7.88 Hz), 8.24 (d, 8 H, J ϭ 10.08 Hz), 8.07 (4 H,
J ϭ 8.12 Hz), 7.79 (d, 1 H, J ϭ 1.48 Hz), 7.75 (t, 2 H, J ϭ 1.72 Hz),
7.71 (d, 1 H, J ϭ 1.72 Hz), 7.68Ϫ7.54 (m, 8 H), 2.56 (s, 6 H). Ϫ
MS (FAB-MS) (nitrobenzyl alcohol matrix); m/z (%): 1093 (15) [M
Ru(bipy)2(dtpH)(PF6)2 (1): A suspension of Ru(bipy)2Cl2·2H2O[17]
(0.065 g, 0.13 mmol) and dtpH (0.046 g, 0.13 mmol) in acetic acid
(10 mL) with 2Ϫ3 drops of N-ethylmorpholine was refluxed under
Ϫ PF6Ϫ], 948 (35) [M Ϫ 2PF6 ϩ eϪ].
Ϫ
Eur. J. Inorg. Chem. 2000, 113Ϫ119
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