Inorganic Chemistry
Article
extracted with ethyl acetate and dried with sodium sulfate, filtered, and
dried by solvent evaporation. The orange liquid obtained corresponds
to 2-methyl-6-(trimethylstannyl)pyridine. Then, this stannate deriva-
tive was used to perform the coupling reaction with 2,6-
dibromopyridine in the presence of LiCl (2 equiv) and Pd(PPh3)4
K) δ = 9.45 (dd, J = 5.9, 1.7 Hz, 4H), 8.06 (m, 11H), 7.63 (ddd, J =
7.3, 5.7, 1.4 Hz, 4H), 7.52 (s, 2H), 2.78 (s, 6H). Elemental analysis (%
found): C, 43.31; H, 3.19; N, 8.11. Calcd for C H F N O S Ru: C,
43.26; H, 3.16; N, 8.14.
PY4Im-Ag (L4). For the synthesis of L4, 2-methylpyridine reacted
31
27
6
5
7 2
(
catalytic amounts) to obtain 6-bromo-6′-methyl-2,2′-bipyridine, as
with 2-fluoropyridine via lithiation in hexanes affording 2-(2-
38
1
39
described elsewhere. Yield: 17%. H NMR (400 MHz, CDCl , 298
pyridylmethyl)pyridine, which was subsequently brominated to
3
4
0
K): δ = 8.62 (m, 2H), 8.30 (m, 2H), 8.26 (d, 1H, J = 7.3 Hz), 8.01 (d,
yield bis(2-pyridyl)bromomethane. This precursor was then added
to a basic solution containing imidazole to obtain (PY4Im)Br, as
1
3
1
1
1
H, J = 6.9 Hz), 7.71 (m, 3H), 7.54 (m, 2H), 7,15 (m, 6H), 2.59 (s,
H), 2.54 (s, 3H). 13C NMR (100 MHz, CDCl , 298 K): δ = 166.5,
previously described by Long and Smith. However, the silver
10
3
65.2, 164.9, 157.5, 156.5, 155.9, 154.9, 154.5, 148.9, 148.7, 136.9,
36.7, 136.7, 136.7, 135.7, 123.9, 123.9, 123.6, 132.5, 123.5, 123.0,
derivative PY4Im-Ag could only be isolated as a pure white powder
when (PY4Im)Br reacted with Ag O in acetonitrile instead of in
2
1
0
21.3, 121.1, 118.3, 118.3, 118.2, 60.7, 27.7, 24.4. ESI-MS (DCM): m/
CH Cl .
2 2
+
II
z = 430.2 ([M + H] ). Elemental analysis (% found): C, 78.21; H,
[Ru (PY4Im)Cl]Cl [7(Cl)]. [PY4ImAg]Br (0.062 g, 0.202 mmol) and
[Ru(p-cymene) (Cl) ] (0.062 g, 0.101 mmol) were dissolved in a
5
.44; N, 16.34. Calcd for C H N : C, 78.30; H, 5.40; N, 16.31.
[
28 23 5
2 2
II
Ru (bpy(bpyMe)PYMe)Cl]Cl [3(Cl)]. A sample of bpy(bpyMe)-
PYMe (0.233 mmol) was dissolved in 5 mL of dry ethanol, and then
1 mg of [Ru(p-cymene) (Cl)2]2 (0.116 mmol) was added. The
flask containing acetonitrile (25 mL), and the resulting solution was
heated under reflux overnight. After that time a yellow precipitate
7
appeared, which was filtered and dried with diethyl ether. Yield: 94 mg
1
mixture was stirred and heated with a MW (300 W) at 150 °C for 1 h.
After this time the volume was reduced in the rotary evaporator. After
(86%). H NMR (400 MHz, DMSO-d , 298 K): δ = 9.42 (d, 4H, J1−2
6
= 5.67 Hz, H1), 7.93 (d, 4H, H4), 7.92 (t, 4H, H3), 7.77 (s, 2H, H12),
7.46 (t, 4H, H2), 7.45 (s, 2H, H6). 13C{ H} NMR (100 MHz,
1
addition of MeOH and 0.5 mL of a NH PF6 saturated aqueous
4
solution, cis-3(Cl) precipitated as a red solid, which was filtered and
DMSO-d , 298 K): δ = 194.78 (C14), 155.63 (C1), 154.91 (C5),
6
1
washed with MeOH and Et O. Yield: 112 mg (68%). H NMR (400
137.20 (C4), 125.67 (C3), 124.40 (C2), 120.51 (C12), 65.19 (C6).
2
+
MHz, d -DCM, 298 K): δ = 9.40 (d, 1H, J = 6.0 Hz), 8.33 (d, 1H, J =
ESI-MS (MeOH): m/z = 541.05([M-Cl] ). Elemental analysis (%
2
8
7
.0 Hz), 8.12 (m, 2H), 8.06 (m, 3H), 7.98 (m, 3H), 7.92 (t, 1H, J =
found): C, 52.10; H, 3.69; N, 14.51. Calcd for C H Cl N Ru: C,
25
21
2
6
.6 Hz), 7.83 (m, 3H), 7.31 (t, 1H, J = 6.4 Hz), 7.22 (t, 1H, J = 6.4
52.00; H, 3.67; N, 14.55.
13
II
Hz), 6.90 (d, 1H, J = 6 Hz), 3.63 (s, 3H), 2.90 (s, 3H). C NMR (100
[Ru (PY4Im)(H O)](BF ) [8(BF ) ]. 7(Cl) (0.060 g, 0.103 mmol)
2 4 2 4 2
MHz, d -DCM, 298 K): δ = 165.6, 161.2, 160.1, 159.0, 158.6, 158.6,
and AgBF (0.061 g, 0.309 mmol) were dissolved in darkness in a flask
2
4
1
1
2
57.7, 156.9, 156.1, 150.6, 137.8, 137.3, 136.1, 135.9, 134.6, 128.3,
25.5, 123.2, 122.8, 122.7, 122.1, 122.0, 121.8, 121.7, 120.5, 57.8, 27.6,
containing acetone/water (10 mL, 1:4). The resulting solution was
stirred and heated under reflux overnight. After it cooled to room
temperature, the solution was filtered to remove the AgCl byproduct.
Slow evaporation of the acetone yielded yellow crystals, which were
−1
−1
1.9. UV/vis (DCM): λmax, nm (ε, M ·cm ) = 292 (29 954), 379
+
(
4787), 502 (5802). ESI-MS (DCM): m/z = 566.1 ([M-Cl] ).
1
Elemental analysis (% found): C, 56.01; H, 3.89; N, 11.59. Calcd for
filtered and dried over air. Yield: 60 mg (84%). H NMR (400 MHz,
D O, 298 K): δ = 9.20 (d, 4H, J1−2 = 5.60 Hz, H1), 7.89 (d, 4H, H4),
2
8
23
II
2
5
2
7.87 (ddd, 4H, H3), 7.62 (s, 2H, H12), 7.44 (ddd, 4H, J2−3 = 7.73
1
3
1
Hz, J2−1 = 5.60 Hz, J2−4 = 2.12 Hz, H2), 7.13 (s, 2H, H6). C{ H}
NMR (100 MHz, D O, 298 K): δ = 195.18 (C14), 154.24 (C1),
4
6
2
153.26 (C5), 137.15 (C4), 125.46 (C3), 124.00 (C2), 119.64 (C12),
precipitate appeared, which was filtered and washed with Et O. Yield:
66.07 (C6). UV/vis (aqueous solution at pH 8, phosphate buffer):
2
1
−1
−1
3
9
2
1
1 mg (86%). H NMR (400 MHz, d -acetone/D O 5:95, 298 K): δ =
λmax, nm (ε, M ·cm ) = 245 (10 270), 360 (6549), 394 (7140).
6
2
2+
.04 (d, 1H, J = 4.8 Hz), 8.27 (t, 2H, J = 7.6 Hz), 8.16 (dd, 1H, J = 6.8,
.4 Hz), 8.01 (m, 6H), 7.81 (m, 5H), 7.28 (t, 1H, J = 6.4 Hz), 7.19 (t,
ESI-MS (MeOH): m/z = 269.0 ([M-2BF −H O+MeOH] ).
4
2
Elemental analysis (% found): C, 43.07; H, 3.35; N, 11.98. Calcd
for C H B F N ORu: C, 43.01; H, 3.32; N, 12.04.
H, J = 6.4 Hz), 7.02 (d, 1H, J = 6 Hz), 3.05 (s, 3H), 2.80 (s, 3H). 13
C
25
23
2
8
6
NMR (100 MHz, d -acetone/D O 5:95, 298 K): δ = 164.2, 161.2,
X-ray Crystal Structure Determination. X-ray crystal structure
determination was made on a Bruker-Nonius diffractometer equipped
with an APPEX II 4K CCD area detector, a FR591 rotating anode with
Mo Kα radiation, Montel mirrors as a monochromatic, and a Kryoflex
low-temperature device (T = −173 °C). Full-sphere data collection
was used with w and f scans. Programs used were as follows: for data
collection, Bruker APPEX II (versions v1.0−22, v2009.1−0 and
v2009.1−02); for data reduction, Bruker SAINT (versions V.2.10, V/
.60A and V7.60A); for absorption corrections, Bruker SADABS
6
2
1
1
1
58.7, 157.9, 157.0, 157.0 156.8, 156.5, 156.0, 151.7, 138.6, 138.2,
38.0, 136.7, 136.3, 128.7, 125.9, 124.2, 124.0, 123.7, 123.0, 122.5,
22.0, 121.4, 121.4, 58.0, 24.9, 20.5. UV/vis (H O): λmax, nm (ε,
2
−1
−1
M ·cm ) = 300 (21 271), 354 (6125), 392 (5709), 521 (5203). ESI-
MS (DCM): m/z = 550.1([M-2PF +2H] ). Elemental analysis (%
+
6
found): C, 40.19; H, 3.03; N, 8.32. Calcd for C H F N OP Ru: C,
28
25 12
5
2
4
0.11; H, 3.01; N, 8.35.
II
[
Ru (PY5Me )Cl]Cl [5(Cl)]. A sample of PY5Me (0.225 mmol) was
2
2
4
1
dissolved in 5 mL of dry ethanol, then 137 mg of [Ru(p-cymene)
Cl) ] (0.225 mmol) was added. The mixture was stirred and heated
(versions V.2.10, V2008 and V2008/1); and for structure refine-
42 43
(
ment, SHELXTL (versions V6.12 and V6.14) and SQUEEZE
44
2
2
with a MW (300 W) at 150 °C during 1 h. After this time the volume
implemented in Platon.
Crystals of 2(PF ) were obtained by slow ether diffusion in an
was reduced in the rotary evaporator. After addition of Et O, a yellow
2
6 2
2+
solid precipitated, which was filtered and washed with Et O. Yield: 103
acetone/water solution of the aqua complex. 2 crystallizes in a cell in
2
1
mg (74%). H NMR (400 MHz, deuterated dimethyl sulfoxide
which the asymmetric unit of this structure contains half a molecule of
(
DMSO-d ), 298 K) δ = 9.67 (dd, J = 5.8, 1.8 Hz, 4H), 8.04 (m, 7H),
the cationic metal complex, which has C symmetry, since the Ru ion
shows a distorted octahedral symmetry, two half PF6 anions, and
6
s
−
7
(
.96 (td, J = 7.8, 1.5 Hz, 4H), 7.53 (ddd, J = 7.3, 5.8, 1.4 Hz, 4H), 2.76
s, 6H). Elemental analysis (% found): C, 56.66; H, 4.12; N, 11.31.
Calcd for C H Cl N Ru: C, 56.59; H, 4.09; N, 11.38.
highly disordered acetone molecules. The cationic metal complex is
coordinated to an oxygen atom, which likely corresponds to a water
molecule in accordance with the number of counteranions and a
2
9
25
2
5
II
[
Ru (PY5Me )(H O)](OTf) [6(OTf) ]. 5(Cl) (40 mg, 0.07 mmol)
2 2 2 2
−
and AgOTf (23 mg, 0.09 mmol) were dissolved in darkness in a flask
containing acetone/water (10 mL, 1:1). The resulting solution was
stirred and heated under reflux for 5 h. After it cooled to room
temperature, the solution was filtered to remove the AgCl byproduct.
Slow evaporation of the acetone yielded a yellow solid, which was
diamagnetic NMR spectrum. The PF6 anions are disordered in
different orientations shared with neighboring asymmetric units. To
avoid the highly disordered acetone molecules the program
4
3
SQUEEZE was applied leading to a refined model with an R1
value of 4.79% in which all the solvent molecules were removed. For
3(Cl), crystals were obtained after slow evaporation of an acetone/
water saturated solution of the chlorido complex. The asymmetric unit
filtered and dried in air. The residue was crystallized by Et O diffusion
into water. Yield: 40 mg (67%). H NMR (400 MHz, DMSO-d , 298
2
1
6
K
Inorg. Chem. XXXX, XXX, XXX−XXX