II
Trinuclear Ru Complexes containing Imidazole Rings
2 3
(0.69 g, 1.95 mmol), and K CO (1.13 g, 8.16 mmol) in DMF (30 mL) tris[(3-formylphenoxy)methyl]benzene to react with 1,10-phenanthro-
were heated to 80 °C for 24 h in a nitrogen atmosphere. After cooling to line-5,6-dione (361 mg, 1.72 mmol). Yield 172 mg (35.6 %) of a yel-
1
room temperature, the solution was diluted with water (300 mL). A color- low solid. H NMR (300 MHz, [D
6
]DMSO): δ = 3.16 (s, 6 H), 4.22
less precipitate was formed and collected by filtration. This precipitate (s, 6 H), 7.05 (d, J = 7.8 Hz, 3 H), 7.40 (t, J = 7.8 Hz, 3 H), 7.68 (dd,
was purified by column chromatography on silica, eluting with J = 7.8, 4.8 Hz, 6 H), 7.77 (d, J = 7.8 Hz, 3 H), 7.86 (s, 3 H), 8.74
CH
2
Cl
2
:CH
3
CH
2
OH (20:1) to afford the desired product as a colorless (d, J = 7.8 Hz, 6 H), 8.91 (d, J = 2.1 Hz, 6 H). LC-MS: m/z 1032.6
1
+
solid. Yield 391 mg (41.8 %). H NMR (300 MHz, CDCl
3
): δ = 5.17 [M + H] . Elemental anal. for C63
H
45
N
13
O
3
: calcd. C 73.31, H 4.39,
(
4
s, 6 H), 7.24 (s, 3 H), 7.43–7.50 (m, 12 H), 9.97 (s, 3 H). LC-MS: m/z N 17.64 %; found: C 73.46, H 4.52, N 17.78 %.
+
+
+
81.0 [M + H] , 498.0 (M + NH
4
] , 503.0 [M + Na] .
1
1
L1 (127 mg,
O (226 mg, 0.43 mmol) in ethylene
[
(bpy)
6
Ru
3
H
3
L ](PF
6
)
6
[RuH
Cl
3
L ](PF
6
)
6
: A mixture of H
3
0
.12 mmol) and Ru(bpy)
2
2
·2H
2
1,3,5-Tris[(3-formylphenoxy)methyl]-2,4,6-trimethylbenzene: The
glycol (20 mL) was heated to 150 °C for 12 h in a nitrogen atmos-
phere. The color of the solution changed to red during the time. After-
wards, the solvent was evaporated under reduced pressure, the residue
was purified twice by column chromatography on alumina eluting first
compound was prepared by the same procedure as described for 1,3,5-
tris[(3-formylphenoxy)methyl]benzene, except 1,3,5-tris(bromo-
methyl)-2,4,6-trimethylbenzene (0.65 g, 1.64 mmol) was used instead
of 1,3,5-tris(bromomethyl)benzene to react with 3-hydroxybenzalde-
with CH
3
CN/ethanol (10:1) to remove impurities, additionally with
hyde (0.71 g, 5.82 mmol). Yield 394 mg (46.0 %) of a colorless solid.
1
1
CH CN/ethanol (5:1) to afford complex [(bpy) Ru H L ]Cl , which
3
6
3
3
6
3
H NMR (300 MHz, CDCl ): δ = 2.47 (s, 9 H), 5.19 (s, 6 H), 7.27–
was dissolved in a minimum amount of water followed by dropwise
7
.30 (m, 3 H), 7.46–7.51 (m, 6 H), 7.56 (s, 3 H), 10.02 (s, 3 H). LC-
+
addition of saturated aqueous NH PF6 until no more precipitate
4
MS: m/z 540.0 (M + NH
4
] .
formed. The precipitate was purified by recrystallization from an aceto-
2
,2',2"-Tris[(3-formylphenoxy)ethyl]amine: The compound was pre- nitrile-diethyl ether mixture (vapor diffusion method) to give a red
1
pared by the same procedure as described for 1,3,5-tris[(3-formylphen- solid. Yield 145 mg (37.9 %). H NMR (300 MHz, [D
6
]DMSO): δ =
oxy)methyl]benzene, except tris(2-chloroethyl)amine hydrochloride 5.38 (s, 6 H), 7.28 (s, 3 H), 7.34 (t, J = 6.6 Hz, 6 H), 7.57–7.62 (m,
(
0.76 g, 3.18 mmol) was used instead of 1,3,5-tris(bromomethyl)ben-
15 H), 7.76 (s, 3 H), 7.85 (d, J = 6.0 Hz, 6 H), 7.89–7.96 (m, 9 H),
zene to react with 3-hydroxybenzaldehyde (1.32 g, 10.82 mmol). Yield 8.04–8.05 (d, 9 H), 8.11 (t, J = 7.8 Hz, 6 H), 8.22 (t, J = 7.8 Hz, 6
1
3
25 mg (22.2 %) of a colorless ropy liquid. H NMR (300 MHz, H), 8.84 (d, J = 8.7 Hz, 6 H), 8.88 (d, J = 8.7 Hz, 6 H), 9.08 (d, J =
2
+
CDCl
3
): δ = 3.21 (t, J = 5.7 Hz, 6 H), 4.17 (t, J = 5.1 Hz, 6 H), 7.14– 6.9 Hz, 6 H). LC-MS: m/z 1434.6 (M – 2PF
6
) , 1362.8 (M – 3PF
6
–
–
2+
3+
3+
7
.16 (m, 3 H), 7.37–7.41 (m, 9 H), 9.95 (s, 3 H). LC-MS: m/z 462.2 H) , 908.3 (M – 3PF
6
) , 860.3 (M – 4PF
6
– H) , 810.5 (M – 5PF
– H) , 572.6 (M – 6PF
H F N O P Ru : calcd. C 47.87, H 2.87, N 10.63 %;
90 36 24 3 6 3
6
+
3+
4+
4+
[
M + H] .
2 H) , 609.1 (M – 5PF
anal. for C126
found: C 47.98, H 3.02, N 10.78 %.
6
6
–2 H) . Elemental
1
,3,5-Tris{3-((1,10-phenanthroline-[5,6-d]imidazol-2-
1
yl)phenoxy)methyl}benzene (H
3
L ): A mixture of 1,3,5-tris[(3-for-
2
2
2
[
(bpy)
6
Ru
3
H
3
L ](PF
6
)
6
[RuH
3
L ](PF
6
)
6
: [RuH
3
L ](PF
6
)
6
was pre-
, except
mylphenoxy)methyl]benzene (282 mg, 0.59 mmol), 1,10-phenanthro-
line-5,6-dione (456 mg, 2.17 mmol), and NH Ac (3.34 g,
3.38 mmol) in glacial acetic acid (45 mL) was heated to 130 °C for
h. A suspension formed during the heating process. The reaction
1
pared by the same procedure as described for [RuH
3
L ](PF
6
)
6
4
2
1
H
3
L
(113 mg, 0.10 mmol) was used instead of H
3
L
to react with
4
3
Ru(bpy)
2
Cl
2
·2H
2
O (192 mg, 0.37 mmol) affording a red solid. Yield
1
152 mg (45.8 %). H NMR (300 MHz, [D
6
]DMSO): δ = 2.52 (s, 9
mixture was filtered hot, subsequently washed with hot ethanol, hot
H), 5.33 (s, 6 H), 7.33 (t, J = 6.3 Hz, 6 H), 7.56–7.58 (m, 15 H), 7.83
(d, J = 4.8 Hz, 12 H), 7.91 (s, 6 H), 8.01 (d, J = 8.1 Hz, 3 H), 8.05–
DMF, and ethyl ether, respectively, to afford the desired product as a
1
yellow solid. Yield 258 mg (41.8 %).
H NMR (300 MHz,
8
.10 (m, 9 H), 8.16–8.22 (m, 9 H), 8.82 (d, J = 8.7 Hz, 6 H), 8.86 (d,
[
6
D ]DMSO): δ = 5.35 (s, 6 H), 7.21 (d, J = 7.8 Hz, 3 H), 7.52 (t, J =
3
+
J = 8.7 Hz, 6 H), 9.05 (s, 6 H). LC-MS: m/z 777.5 (M – 6PF
6
–3 H) ,
8
7
1
.1 Hz, 3 H), 7.72 (s, 3 H), 7.76 (s, 6 H), 7.88 (d, J = 7.8 Hz, 3 H),
4
+
4+
4+
6
56.6 (M – 4PF
495.5 (M – 5PF
Elemental anal. for C129
0.49 %; found: C 48.52, H 3.13, N 10.63 %.
6
) , 619.3 (M – 5PF
6
– H) , 582.8 (M – 6PF
6
–2 H) ,
.99 (s, 3 H), 8.88 (t, J = 4.5 Hz, 6 H), 8.99 (s, 3 H), 9.00 (s, 3 H),
5
+
5+
6+
+
6
) , 466.8 (M – 6PF
6
– H) , 389.4 (M – 6PF
6
) .
3.67 (s, 3 H). LC-MS: m/z 1051.6 [M + H] . Elemental anal. for
96 36 24 3 6 3
H F N O P Ru : calcd. C 48.37, H 3.02, N
66 42 12 3
C H N O : calcd. C 75.42, H 4.03, N 15.99 %; found: C 75.56, H
1
4.15, N 16.12 %.
3
3
3
[
(bpy)
6
Ru
3
H
3
L ](PF
6
)
6
[RuH
3
L ](PF
6
)
6
: [RuH
3
L ](PF
6
)
6
was pre-
, except
1
,3,5-Tris{3-((1,10-phenanthroline-[5,6-d]imidazol-2-
1
pared by the same procedure as described for [RuH
3
L ](PF
6
)
6
2
L2 was pre-
yl)phenoxy)methyl}-2,4,6-trimethylbenzene (H
3
L ): H
3
3
1
H
3
L
(132 mg, 0.13 mmol) was used instead of H
3
L
to react with
1
pared by the same procedure as described for H
tris[(4-formylphenoxy)methyl]-2,4,6-trimethylbenzene
.35 mmol) was used instead of 1,3,5-tris[(3-formylphen-
3
L , except 1,3,5-
Ru(bpy)
2
Cl
2
·2H
2
O (239 mg, 0.46 mmol) affording a red solid. Yield
(183 mg,
1
167 mg (41.5 %). H NMR (300 MHz, [D
6
]DMSO): δ = 3.26 (s, 6
0
H), 4.34 (s, 6 H), 7.16 (d, J = 8.1 Hz, 3 H), 7.31–7.37 (m, 6 H), 7.47
t, J = 7.8 Hz, 3 H), 7.55–7.67 (m, 15 H), 7.69 (t, J = 6.3 Hz, 3 H),
oxy)methyl]benzene to react with 1,10-phenanthroline-5,6-dione
(
1
(
273 mg, 1.30 mmol). Yield 175 mg (45.7 %) of a yellow solid. H
7
7
.73–7.84 (m, 9 H), 7.91 (s, 3 H), 7.96–8.00 (m, 6 H), 8.09 (t, J =
.5 Hz, 6 H), 8.20 (t, J = 7.8 Hz, 6 H), 8.82–8.88 (m, 18 H) ppm. LC-
NMR (400 MHz, [D
6
]DMSO): δ = 2.39 (s, 9 H), 5.14 (s, 6 H), 7.22
(
d, J = 7.8 Hz, 3 H), 7.59 (t, J = 7.8 Hz, 3 H), 7.82 (s, 6 H), 7.94 (s,
3+
3+
MS: m/z 903.6 (M – 3PF
4
6
) , 853.1 (M – 4PF
6
– H) , 641.2 (M –
3
3
H), 7.97 (d, J = 4.8 Hz, 3 H), 8.95 (d, J = 7.8 Hz, 6 H), 9.02 (d, J =
.9 Hz, 6 H), 13.79 (s, 3 H). LC-MS: m/z 1093.4 [M + H] . Elemental
4+
4+
4+
PF
PF
6
) , 604.1 (M – 5PF
6
– H) , 567.3 (M – 6PF
– H) , 379.1 (M – 6PF
6
–2 H) , 483.5 (M –
6
+
5+
5+
6+
5
6
) , 454.3 (M – 6PF
6
) . Elemental anal.
48 12 3
anal. for C69H N O : calcd. C 75.81, H 4.43, N 15.38 %; found: C
93 36 25 3 6 3
for C123H F N O P Ru : calcd. C 47.02, H 2.98, N 11.14 %; found:
C 47.15, H 3.10, N 11.27 %.
75.96, H 4.56, N 15.49 %.
2
,2',2"-Tris{3-((1,10-phenanthroline-[5,6-d]imidazol-2-
3
3
yl)phenoxy)ethyl}amine (H
3
L ): H
3
L was prepared by the same pro-
Supporting Information (see footnote on the first page of this article):
1
1
II
cedure as described for H
3
L , except 2,2',2"-tris[(3-formylphen-
H NMR and mass spectra of the ligands and corresponding Ru com-
oxy)ethyl]amine (216 mg, 0.47 mmol) was used instead of 1,3,5- plexes are included.
Z. Anorg. Allg. Chem. 2011, 766–772
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
767