1
2
N.V. Nair et al. / Inorganica Chimica Acta xxx (2016) xxx–xxx
(
2
(
(
9
m, 7H), 8.73 (d, 2H, J = 7.8 Hz), 8.61 (d, 2H, J = 7.8 Hz), 8.55 (m,
H), 8.40 (m, 1H), 8.23 (m, 6H), 8.02 (m, 8H), 7.88 (m, 2H), 7.88
m, 1H), 7.65 (m, 2H), 7.58 (d, 1H, J = 5.5 Hz), 7.45 (m, 4H), 7.16
vacuum to provide 6 as a tan-colored solid (240 mg, 70%): mp
220 °C dec; H NMR (500 MHz,CDCl ) d 9.23 (m, 2H), 8.85 (s, 2H),
3
8.75 (d, 2H, J = 4.01 Hz), 8.71 (d, 2H, J = 9.16 Hz), 8.32 (m, 2H),
1
m, 1H). Anal. Calc for C57
H
41
F
18
N
11
P
3
Ru
2
: C, 41.64; H, 2.51 N,
8.10 (d, 2H, J = 8.02 Hz), 7.91 (dt, 2H, J = 8.02, 1.72 Hz), 7.83 (s,
13
.37. Found: C, 41.78 H, 2.90; N, 8.98%. MS (ESI): m/z 1499.97
1H), 7.69 (m, 3H), 7.63 (m, 1H), 7.38 (m, 2H);
(125 MHz, DMSO-d ) d 156.4, 155.4, 150.8, 150.4, 149.9, 149.5,
46.4, 145.7, 140.1, 138.1, 137.9, 137.6, 136.9, 134.6, 131.5,
128.4, 127.8, 127.6, 127.5, 125.2, 124.3, 123.9, 121.5, 118.5.
C NMR
+
2+
3+
(
MꢁPF
6
) , 677.49 (Mꢁ2PF
6
)
, 403.35 (Mꢁ3PF
6
)
.
6
1
4
.2.2. Ligand 5
A mixture of 13 (315 mg, 1.01 mmol), 16 (205 mg, 1.01 mmol)
and Pd(PPh (96 mg, 8 mol%) in a pressure tube was suspended
in n-propylamine (10 mL) and degassed with N for 15 min. The
3
)
4
4.2.3.1. [Ru(bpy)
2
(6)](PF
, 6 (100 mg, 0.205 mmol) was treated with
] (107 mg, 0.205 mmol) to afford [Ru(bpy) (6)](PF
6 2
) . Following the same procedure as
2
[Ru(bpy)
[Ru(bpy)
2
(4)](PF
6 2
)
tube was sealed and heated at 80 °C for 24 h. By this time a brown
precipitate had formed, which was collected and washed with
2
Cl
2
2
6 2
)
1
6
as an orange solid (61 mg, 25%): H NMR (400 MHz, acetone-d )
water (20 mL), EtOH (20 mL) and Et
2
O (5 mL) before drying under
d 8.83 (d, 2H, J = 5.7 Hz), 8.71 (m, 4H), 8.61 (d, 1H, J = 8.2 Hz),
8.50 (m, 5H), 8.25 (d, 1H, J = 8.5, 3.2 Hz), 8.09 (m, 6H), 7.98 (m,
4H), 7.84 (d, 2H, J = 5.5 Hz), 7.77 (m, 3H), 7.68 (m, 1H), 7.58 (m,
2H), 7.43 (m, 4H), 7.24 (m, 2H).
vacuum to provide 5 as a brown solid (230 mg, 81%): mp 202–
1
2
08 °C; H NMR (500 MHz, CDCl
3
) d 9.32 (d, 1H, J = 3.4 Hz), 9.27
(
d, 1H, J = 2.3 Hz), 8.99 (d, 1H, J = 7.4 Hz), 8.80 (m, 4H), 8.72 (d,
1
7
H, J = 8.0 Hz), 8.33 (d, 1H, J = 8.6 Hz), 8.22 (s, 2H), 7.98 (m, 2H),
.86 (m, 1H), 7.73 (dd, 1H, J = 8.0, 4.6 Hz), 7.45 (m, 2H); 13C NMR
4.2.3.2. [Ru(bpy)
dure as [Ru(bpy)
0.046 mmol) was treated with [Ru(bpy)(dmso)
0.045 mmol) to provide [Ru(bpy) (6)Ru(bpy)Cl](PF
solid (10 mg, 13%): H NMR (500 MHz, acetone-d ) d 10.34 (d, 1H,
2
(6)Ru(bpy)Cl](PF
6 3
) . Following the same proce-
(
1
1
125 MHz, DMSO-d
45.8, 138.2, 137.1, 134.9, 133.6, 132.6, 128.3, 127.9, 125.5,
24.7, 124.5, 122.7, 121.5, 118.2, 93.0, 90.8.
6
) d 156.1, 154.7, 151.9, 151.3, 150.0, 146.3,
2
(4)Ru(bpy)Cl](PF
6
)
2, [Ru(bpy)
2
(6)](PF (55 mg,
6
)
2
2
Cl ] (22 mg,
2
2
6 3
) as a maroon
1
6
4
.2.2.1. [Ru(bpy)
2
(5)](PF
2, 5 (100 mg, 0.23 mmol) was treated with
] (119 mg, 0.23 mmol) to afford [Ru(bpy) (5)](PF
6
)
2
. Following the same procedure as
J = 4.6 Hz), 9.19 (s, 2H), 8.84 (m, 9H), 8.70 (d, 1H, J = 8.6 Hz), 8.59
(d, 1H, J = 8.6 Hz), 8.53 (d, 1H, J = 8.6 Hz), 8.49 (m, 3H), 8.37 (m,
1H), 8.25 (m, 2H), 8.16 (m, 4H), 8.08 (m, 1H), 7.98 (m, 9H), 7.84
(d, 1H, J = 5.1 Hz), 7.81 (m, 1H), 7.65 (m, 3H), 7.42 (m, 4H), 7.10
(m, 1H).
[
[
Ru(bpy)
Ru(bpy)
2 6
(4)](PF )
2
Cl
2
2
6 3
)
1
as an orange solid (96 mg, 37%): H NMR (400 MHz, acetone-d
d 9.31 (d, 1H, J = 8.24 Hz), 8.92 (s, 1H), 8.84 (m, 5H), 8.75 (m,
6
)
6
8
2
H), 8.55 (d, 1H, J = 5.5 Hz), 8.51 (d, 1H, J = 5.5 Hz), 8.26 (m, 2H),
.16 (m, 4H), 8.06 (m, 3H), 7.96 (m, 3H), 7.64 (m, 2H), 7.52 (m,
H), 7.40 (m, 2H).
4.2.3.3. [Ru(bpy)
as [Ru(bpy) (4)Ru(bpy)I](PF
.006 mmol) was treated with KI (50 mg, 0.301 mmol) to afford
2
(6)Ru(bpy)I](PF
6
)
3
. Following the same procedure
2
6
)
2
, [Ru(bpy)
2
(6)Ru(bpy)Cl](PF (10 mg,
6 3
)
0
1
4
.2.2.2. [Ru(bpy)
2
(5)Ru(bpy)Cl](PF
(4)Ru(bpy)Cl](PF
.03 mmol) and [Ru(bpy)(dmso) Cl
6 3
)
. Following the same proce-
2, [Ru(bpy) (5)](PF (38 mg,
] (16 mg, 0.03 mmol) were
[Ru(bpy)
2
(6)Ru(bpy)I](PF
6
)
3
(8 mg, 82%):
H NMR (500 MHz,
dure as [Ru(bpy)
0
2
6
)
2
6
)
2
acetone-d ) d 10.78 (d, 1H, J = 5.0 Hz), 9.24 (s, 2H), 8.86 (m, 8H),
6
2
2
8.71 (d, 1H, J = 7.3 Hz), 8.57 (m, 3H), 8.51 (m, 3H), 8.39 (m, 1H),
8.27 (m, 2H), 8.18 (m, 4H), 7.98 (m, 11H), 7.88 (m, 1H), 7.65 (m,
2H), 7.54 (d, 1H, J = 5.0 Hz), 7.44 (m, 4H), 7.17 (m, 1H). Anal. Calc.
reacted to provide a crude solid which was then purified twice
by column chromatography on alumina, eluting with MeOH/ace-
tone (4:100) to provide [Ru(bpy)
2
(5)Ru(bpy)Cl](PF
solid (7 mg, 15%): H NMR (400 MHz, acetone-d ) d 10.38 (d, 1H,
J = 5.0 Hz), 9.80 (d, 1H, J = 8.7 Hz), 9.53 (s, 1H), 9.31 (s, 1H), 8.87
6
)
3
as a maroon
for C63
45 18 11 3 2
H F N P Ru : C, 43.99; H, 2.64; N, 8.96. Found: C,
1
+
6
44.05; H, 3.00; N, 8.65%. MS (ESI): m/z 1575.99 (MꢁPF
6
) , 715.46
2
+
3+
(Mꢁ2PF
6
)
, 428.75 (Mꢁ3PF
6
) .
(
(
m, 9H), 8.59 (d, 1H, J = 8.2 Hz), 8.44 (m, 3H), 8.26 (m, 2H), 8.25
m, 2H), 8.14 (m, 7H), 8.01 (d, 1H, J = 5.5 Hz), 7.92 (dd, 1H, J = 8.2,
4.2.4. Ligand 7
4
.1 Hz), 7.80 (m, 4H), 7.64 (m, 2H), 7.58 (d, 1H, J = 5.0 Hz), 7.49
To a mixture of 16 (205 mg, 1 mmol), 17 (323.5 mg, 0.83 mmol)
and Pd(PPh (96 mg, 8 mol%) in a pressure tube was added
n-propylamine (20 mL) and the mixture was degassed with N
(
t, 1H, J = 6.4 Hz), 7.42 (m, 1H), 7.36 (m, 1H), 7.06 (m, 2H).
3 4
)
2
4
.2.2.3. [Ru(bpy)
as [Ru(bpy) (4)Ru(bpy)I](PF
7 mg, 0.004 mmol) was treated with KI (50 mg, 0.301 mmol) to
2
(5)Ru(bpy)I](PF
6
)
3
. Following the same procedure
for 15 min. The tube was then sealed and heated at 80 °C for
40 h. The reaction mixture was cooled and the precipitate which
had formed was filtered, washed with water (20 mL), EtOH
(20 mL) and diethyl ether (10 mL) and dried under vacuum to
2
6
)
3
,
[Ru(bpy) (5)Ru(bpy)Cl](PF
2
6 3
)
(
1
afford [Ru(bpy)
2
(5)Ru(bpy)I](PF
6
)
3
(5 mg, 75%):
H
NMR
1
(
400 MHz, acetone-d
6
) d 10.75 (d, 1H, J = 5.7 Hz), 9.35 (d, 1H,
afford 7 as a tan solid (280 mg, 66%): mp >260 °C; H NMR
J = 8.0 Hz), 9.06 (s, 2H), 8.86 (m, 8H), 8.71 (m, 2H), 8.59 (d, 1H,
J = 8.0 Hz), 8.53 (d, 1H, J = 5.1 Hz), 8.51 (d, 1H, J = 5.7 Hz), 8.26
3
(500 MHz, CDCl ) d 9.26 (d, 1H, J = 4.1 Hz), 9.21 (d, 1H, J = 4.1 Hz),
8.88 (d, 1H, J = 8.2 Hz), 8.80 (s, 2H), 8.76 (d, 2H, J = 4.1 Hz), 8.70
(d, 2H, J = 7.8 Hz), 8.26 (d, 1H, J = 7.5 Hz), 8.15 (s, 1H), 8.0 (d, 2H,
(
m, 2H), 8.16 (m, 4H), 8.05 (m, 2H), 7.98 (m, 7H), 7.87 (m, 1H),
.64 (m, 2H), 7.52 (d, 1H, J = 5.7 Hz), 7.42 (m, 4H), 7.16 (m, 1H).
Anal. Calcd for C59 Ru : C, 42.48; H, 2.48; N, 9.24.
7
J = 7.3 Hz), 7.91 (t, 2H, J = 7.3 Hz), 7.80 (m, 3H), 7.39 (m, 2H); 13
C
H
41
F
18
N
11
P
3
2
3
NMR (125 MHz, CDCl ) d 156.2, 151.1, 150.8, 149.3, 146.3, 146.1,
139.0, 137.1, 135.9, 134.9, 132.4, 130.9, 128.4, 128.2, 127.6,
124.1, 123.6, 123.4, 121.5, 119.9, 118.8, 95.2, 87.3.
+
Found: C, 42.86 H, 2.87 N, 8.96%. MS (ESI): m/z 1522.97 (MꢁPF
6
) ,
2
+
3+
6
4
0
89.47 (Mꢁ2PF
6
)
, 411.02 (Mꢁ3PF
6
) .
.2.3. Ligand 6
4.2.4.1. [Ru(bpy)
2
(7)](PF
2, 7 (100 mg, 0.195 mmol) was treated with
] (101 mg, 0.195 mmol) to afford [Ru(bpy) (7)](PF
6 2
) . Following the same procedure as
To
a
mixture of 18 (274 mg, 0.63 mmol), 15 (163 mg,
)Cl (22 mg, 5 mol%) and anhyd. CO
[Ru(bpy)
[Ru(bpy)
2
(4)](PF
6
)
.63 mmol), Pd(PPh
3
2
K
2
3
2
Cl
2
2
6 2
)
1
(
261 mg, 1.89 mmol) was added dry DMSO (5 mL) and degassed
for 15 min. The mixture was then heated at 100 °C for 24 h. After
cooling, H O (10 mL) was added to the reaction mixture and the
precipitate that had formed was collected and washed with H
20 mL), EtOH (20 mL), acetone (5 mL) and allowed to dry under
6
as an orange solid (101 mg, 43%): H NMR (500 MHz, acetone-d )
d 9.21 (d, 1H, J = 8.2 Hz), 8.83 (m, 7H), 8.74 (m, 5H), 8.51 (d, 1H,
J = 5.0 Hz), 8.46 (d, 1H, J = 5.5 Hz), 8.24 (m, 2H), 8.15 (m, 4H),
8.10 (m, 3H), 8.01 (m, 5H), 7.94 (m, 3H), 7.62 (m, 2H), 7.48 (m,
2H), 7.38 (m, 2H).
2
2
O
(