Inorganic Chemistry
Article
(m, 2H), 8.72 (d, 3J = 7.9 Hz), 8.27 (d, 3J = 8.6 Hz, 2H), 7.93 (tt, 3J =
7.7 Hz, 4J = 1.9 Hz, 2H), 7.69 (d, 3J = 8.6 Hz, 2H), 7.46 (ddd, 3J = 7.5
Hz, 3J = 4.7 Hz, 4J = 1.0 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3):
δ 164.8, 164.7, 164.0, 155.5, 154.2, 150.3, 149.6, 137.3, 137.0, 136.1,
132.3, 129.3, 125.9, 125.8, 125.0, 124.3, 122.6, 111.9. ESI-MS. Calcd
for C20H13BrN4 ([M + H]+): m/z 389.03966. Found: m/z 389.03964.
Difference: 0.1 ppm.
7.9 Hz, 1H), 8.83 (d, J = 8.0 Hz, 1H), 8.64 (m, 4H), 8.12 (d, J = 8.1
Hz, 2H), 8.05 (t, J = 7.6 Hz, 2H), 7.99−7.93 (m, 4H), 7.60−7.57 (m,
3H), 7.53 (d, J = 5.3 Hz, 1H), 7.42 (d, J = 5.5 Hz, 2H), 7.31 (m, 2H),
7.14 (t, J = 6.6 Hz, 2H), 2.55 (s, 3H). 13C{1H} NMR (126 MHz,
CD3CN): δ 164.45, 163.16, 162.42, 159.13, 157.43, 157.03, 156.25,
154.27, 154.02, 153.72, 149.82, 142.12, 139.42, 139.19, 139.15,
136.01, 134.73, 133.70, 131.25, 130.56, 129.94, 129.87, 128.63,
128.30, 127.55, 127.41, 127.30, 125.49, 122.37, 114.65, 21.37. ESI-
MS. Calcd for C42H30BrN7Ru ([M]2+): m/z 406.53893. Found: m/z
406.54001. Difference: 2.7 ppm. Anal. Calcd for C42H30BrF12N7P2Ru:
C, 45.71; H, 2.74; N, 8.88. Found: C, 46.34; H, 2.83; N, 8.85.
[Ru(Tolyltpy)(L2)](PF6)2 (Ru2). A suspension of [RuCl3(Tolyltpy)]
(185 mg, 429 μmol, 1 equiv), L2 (200 mg, 429 μmol, 1 equiv), and 4
drops of N-ethylmorpholine in 15.0 mL of ethylene glycol was heated
to 180 °C for 15 min using microwave irradiation. After cooling to
room temperature, water and an aqueous potassium hexafluorophos-
phate solution were added to the solution, and the precipitate was
filtered off over Celite. After washing with water, it was dissolved in
MeCN and dried over magnesium sulfate, and the solvent was
removed under reduced pressure. The product was purified by
column chromatography (silica; 7:1 MeCN/aqueous KNO3) to yield
2-[6-(4-Bromophenyl)-2-(pyridin-2-yl)pyrimidin-4-yl]-4,4′-bipyri-
dine (L2). A suspension of I2 (270 mg, 739 μmol, 1 equiv), potassium
hydroxide (62.2 mg, 1.11 mmol, 1.5 equiv), and I5 (128 mg, 813
μmol, 1.1 equiv) in 20.0 mL of ethanol was heated to reflux for 3 days.
After cooling to room temperature, water was added, and the
precipitate was filtered off over Celite, washed with water, and
dissolved in dichloromethane. The organic solution was dried over
magnesium sulfate, and the solvent was reduced under vacuum. The
crude product was washed with hot methanol to yield the product as
1
an off-white solid (102 mg, 219 μmol, 29.6%). H NMR (500 MHz,
CDCl3): δ 9.00 (d, 4J = 1.0 Hz, 1H), 8.90 (m, 3H), 8.80 (dd, 3J = 4.5
Hz, 4J = 1.6 Hz, 2H), 8.71 (d, 3J = 7.9 Hz, 1H), 8.29 (d, 3J = 8.6 Hz,
2H), 7.95 (td, 3J = 7.8 Hz, 4J = 1.7 Hz, 1H), 7.70 (m, 5H), 7.48 (dd,
4
3J = 6.9 Hz, J = 5.3 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3): δ
1
a dark-red solid (150 mg, 136 μmol, 31.7%). H NMR (500 MHz,
165.0, 164.3, 164.1, 155.3, 150.9, 150.4, 150.3, 147.2, 145.5, 137.1,
135.9, 132.3, 129.3, 126.1, 125.1, 124.4, 123.4, 121.8, 120.2, 112.2.
ESI-MS. Calcd for C25H16BrN5 ([M + H]+): m/z 466.06618. Found:
m/z 466.06765. Difference: 3.2 ppm.
CD3CN): δ 9.31 (s, 1H), 9.12 (s, 1H), 9.03 (s, 2H), 8.96 (d, 3J = 7.9
3
3
Hz, 1H), 8.78 (d, J = 4.9 Hz, 2H), 8.66 (m, 4H), 8.14 (d, J = 7.5
Hz, 2H), 8.06 (t, 3J = 7.7 Hz, 1H), 8.00 (d, 3J = 7.6 Hz, 2H), 7.96 (t,
3J = 7.8 Hz, 2H), 7.75 (d, 3J = 5.0 Hz, 2H), 7.70 (d, 3J = 6.0 Hz, 1H),
2-[6-(4-bromophenyl)-4-(pyridin-2-yl)pyrimidin-2-yl]-4,4′-bipyri-
dine (L3). A suspension of I1 (123 mg, 426 μmol, 1 equiv), I6 (100
mg, 426 μmol, 1 equiv), and potassium hydroxide (35.9 mg, 639
μmol, 1.5 equiv) in 15.0 mL of ethanol was heated to reflux for 3 days.
After cooling to room temperature, water was added, and the
precipitate was filtered off over Celite, washed with water, and
dissolved in dichloromethane. The organic solution was dried over
magnesium sulfate, and the solvent was reduced under vacuum. The
crude product was recrystallized from hot methanol to yield the
3
3
7.61 (m, 3H), 7.54 (d, J = 5.5 Hz, 1H), 7.45 (d, J = 5.6 Hz, 2H),
3
3
7.34 (t, J = 6.5 Hz, 1H), 7.16 (t, J = 6.6 Hz, 2H), 2.55 (s, 3H).
13C{1H} NMR (176 MHz, CD3CN): δ 164.54, 163.13, 162.51,
159.14, 158.28, 156.97, 156.23, 154.7, 154.0, 153.8, 151.8, 150.0,
148.1, 143.5, 142.2, 139.5, 139.3, 136.0, 134.7, 133.8, 131.3, 130.5,
130.0, 128.7, 128.4, 127.7, 127.4, 127.2, 125.5, 125.3, 122.5, 114.9,
21.4. ESI-MS. Calcd for C47H33BrN8Ru ([M]2+): m/z 445.0522.
Found: m/z 445.05327. Difference: 2.4 ppm. Anal. Calcd for
C47H33BrF12N8P2Ru: C, 47.81; H, 2.82; N, 9.49. Found: C, 47.91;
H, 2.91; N, 9.79.
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product as an off-white solid (56.0 mg, 120 μmol, 28.2%). H NMR
3
5
(300 MHz, CDCl3): δ 9.03 (dd, J = 5.1 Hz, J = 0.8 Hz, 1H), 8.94
(dd, 4J = 1.8 Hz, 5J = 0.8 Hz, 1H), 8.87 (s, 1H), 8.82 (dd, 3J = 4.4 Hz,
[Ru(Tolyltpy)(L3)](PF6)2 (Ru3). A suspension of [RuCl3(Tolyltpy)]
(59.2 mg, 112 μmol, 1 equiv), L3 (52.0 mg, 112 μmol, 1 equiv), and
silver nitrate (56.8 mg, 335 μmol, 3 equiv) in 15.0 mL of ethylene
glycol was heated to 150 °C for 15 min using microwave irradiation.
After cooling to room temperature, 1−2 mL of hydrazine hydrate,
water, and an aqueous potassium hexafluorophosphate solution were
added to the solution, and the precipitate was filtered off over Celite.
After washing with water, it was dissolved in MeCN and dried over
magnesium sulfate, and the solvent was removed under reduced
pressure. The product was purified by column chromatography
(silica; 12:1 MeCN/aqueous KNO3) to yield a dark-red solid (65.0
4J = 0.8 Hz, 1H), 8.78 (m, 2H), 8.28 (d, J = 8.8 Hz, 2H), 7.94 (m,
3
3
3
4
1H), 7.94 (m, 5H), 7.47 (ddd, J = 7.6 Hz, J = 4.9 Hz, J = 1.1 Hz,
1H). 13C{1H} NMR (100 MHz, CDCl3): δ 164.8, 164.6, 163.5, 156.4,
153.9, 151.0, 150.8, 149.5, 146.7, 145.7, 137.3, 135.8, 132.2, 129.2,
125.9, 125.7, 122.5, 122.4, 121.9, 121.6, 112.1. ESI-MS. Calcd for
C25H16BrN5 ([M + H]+): m/z 466.06618. Found: 466.06794.
Difference: 3.8 ppm.
2,2″-[6-(4-Bromophenyl)pyrimidine-2,4-diyl]di(4,4′-bipyridine)
(L4). A suspension of I2 (100 mg, 274 μmol, 1 equiv), I6 (64.3 mg,
274 μmol, 1 equiv), and potassium hydroxide (46.1 mg, 821 μmol, 3
equiv) in 10.0 mL of ethanol was heated to reflux for 2 days. After
cooling to room temperature, water was added, and the precipitate
was separated and washed with water using a centrifuge to yield the
1
mg, 55.1 μmol, 49.2%). H NMR (500 MHz, CD3CN): δ 9.22 (s,
3
3
1H), 9.20 (d, J = 1.6 Hz, 1H), 9.04 (s, 2H), 8.86 (d, J = 8.0 Hz,
1H), 8.76 (d, 3J = 5.6 Hz, 2H), 8.70 (d, 3J = 8.6 Hz, 2H), 8.68 (d, 3J =
8.1 Hz, 2H), 8.14 (d, 3J = 8.1 Hz, 2H), 8.07 (td, 3J = 7.9 Hz, 4J = 1.3
Hz, 1H), 7.96 (m, 4H), 7.75 (dd, 3J = 4.7 Hz, 4J = 1.5 Hz, 2H), 7.62
(m, 5H), 7.44 (d, 3J = 4.9 Hz, 2H), 7.32 (m, 1H), 7.16 (ddd, 3J = 7.2
1
product as an off-white solid (21.0 mg, 38.6 μmol, 14.1%). H NMR
(500 MHz, CDCl3): δ 9.03 (d, 3J = 5.0 Hz, 1H), 9.00 (s, 1H), 8.92 (s,
2H), 8.90 (d, 3J = 5.0 Hz, 1H), 8.87 (s, 1H), 8.81 (m, 4H), 8.28 (d, 3J
= 8.5 Hz, 2H), 7.70 (m, 8H). 13C{1H} NMR (126 MHz, CDCl3): δ
165.0, 164.6, 163.8, 156.5, 155.2, 151.1, 151.0, 150.9, 150.5, 147.3,
146.9, 145.8, 145.5, 135.8, 132.4, 129.3, 126.2, 123.5, 122.7, 122.1,
121.8, 121.7, 120.3, 112.6. ESI-MS. Calcd for C30H19BrN6 ([M +
H]+): m/z 543.09273. Found: m/z 543.0906. Difference: 3.9 ppm.
[Ru(Tolyltpy)(L1)](PF6)2 (Ru1; CCDC 1997105). A suspension of
[Ru(Tolyltpy)Cl3] (68.2 mg, 128 μmol, 1 equiv) and L1 (50.0 mg,
128 μmol, 1 equiv) in 7.00 mL of ethylene glycol was heated to 180
°C for 15 min using microwave irradiation. After cooling to room
temperature, water and an aqueous potassium hexafluorophosphate
solution were added to the solution. The precipitate was filtered off
over Celite, washed with deionized water, and dissolved in acetonitrile
(MeCN). The solution was dried over magnesium sulfate, and the
solvent was removed under reduced pressure. The crude product was
purified by column chromatography (silica; 7:1 MeCN/aqueous
3
4
Hz, J = 5.7 Hz, J = 1.1 Hz 2H), 2.55 (s, 3H). 13C{1H} NMR (126
MHz, CD3CN): δ 164.4, 163.2, 162.5, 159.1, 157.9, 157.4, 156.2,
154.5, 154.3, 153.8, 151.7, 150.0, 148.5, 143.5, 142.1, 139.3, 139.3,
135.9, 134.7, 133.6, 131.3, 130.8, 129.9, 128.6, 128.3, 127.7, 127.5,
127.3, 125.5, 124.7, 122.6, 122.5, 114.8, 21.4. ESI-MS. Calcd for
C47H33BrN8Ru ([M]2+): m/z 446.05118. Found: m/z 446.05341.
Difference: 2.0 ppm. Anal. Calcd for C47H33BrF12N8P2Ru: C, 47.81;
H, 2.82; N, 9.49. Found: C, 47.34; H, 2.99; N, 9.35.
[Ru(Tolyltpy)(L4)](PF6)2 (Ru4; CCDC 1997099). A suspension of
[RuCl3(Tolyltpy)] (37.1 mg, 69.9 μmol, 1 equiv), L4 (38.0 mg, 39.9
μmol, 1 equiv), and silver nitrate (35.6 mg, 210 μmol, 3 equiv) in 15.0
mL of ethylene glycol was heated to 150 °C for 15 min using
microwave irradiation. After cooling to room temperature, 1−2 mL of
hydrazine hydrate, water, and an aqueous potassium hexafluorophos-
phate solution were added to the solution, and the precipitate was
filtered off over Celite. After washing with water, it was dissolved in
MeCN and dried over magnesium sulfate, and the solvent was
1
KNO3) to yield a dark-red solid (122 mg, 111 μmol, 86.4%). H
NMR (500 MHz, CD3CN): δ 9.17 (s, 1H), 9.02 (s, 2H), 8.94 (d, J =
C
Inorg. Chem. XXXX, XXX, XXX−XXX