Organometallics
Article
(2 × 50 mL), dried with MgSO4, and dried in vacuo to yield a tan
powder. Purification by column chromatography using a CH2Cl2/
EtOAc gradient [SiO2: CH2Cl2/EtOAc, 9:1; Rf = 0.93] and
recrystallization in EtOH yielded 2.19 g (56.8%) of the product as
an off-white solid. 1H NMR (CDCl3): δ 8.66 (d, 1H, 3J = 4.1 Hz, Ha),
mmol) and P8 (500 mg, 1.35 mmol) in THF/water (9:1; 125 mL)
was sparged with N2 for 10 min, K2CO3 (933 mg, 6.73 mmol) and
Pd(PPh3)4 (109 mg, 0.09 mmol) were added, and the reaction was left
to reflux for 14 h under N2. The reaction mixture was then cooled and
poured into H2O. The product was extracted with Et2O (3 × 75 mL)
and washed with brine (3 × 100 mL). The organic layer was dried with
MgSO4 prior to the removal of the solvent in vacuo. The residual
brown oil was purified by column chromatography [SiO2: CH2Cl2/
EtOAc (9:1); Rf = 0.94] to yield 702 mg (93.8%) of the product as a
bright yellow solid. 1H NMR (CDCl3): δ 8.72 (d, 1H, 3J = 4.8 Hz, Ha),
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8.55 (d, 1H, J = 8.0 Hz, Hd), 8.45 (d, 1H, J = 1.2 Hz, He), 8.09 (s,
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1H, Hr), 7.87 (m, 1H, Hn), 7.81 (dt, 1H, J = 7.6, J = 1.5 Hz, Hc),
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7.69 (d, 1H, J = 1.2 Hz, Hm), 7.40−7.36 (m, 2H, Hp, Ho), 7.33 (d,
1H, 3J = 3.9 Hz, Hf), 7.29 (t, 1H, 3J = 5.9 Hz, Hb), 7.05 (d, 1H, 3J = 3.8
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3
Hz, Hg), 3.02 (q, 2H, J = 7.3 Hz, −SCH2CH3), 1.36 (t, 3H, J = 7.3
Hz, −SCH2CH3). 13C NMR (CDCl3): δ 156.8, 156.6, 155.8, 149.1,
143.2, 142.3, 139.7, 137.4, 137.0, 131.3, 129.7, 129.3, 127.8, 125.9,
124.6, 124.1, 121.5, 116.2, 115.4, 114.3, 27.9, 14.5. HRMS (EI): m/z
454.0005 [(M)+] (calcd for C22H17BrN2S2 m/z 453.9996).
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8.63 (d, 1H, J = 8.0 Hz, Hd), 8.61 (d, 1H, J = 1.5 Hz, He), 8.17 (s,
1H, Hn), 7.96 (dt, 1H, 3J = 6.6, 4J = 2.2 Hz, Hr), 7.89 (d, 1H, 4J = 1.5
Hz, Hm), 7.85 (dt, 1H, 3J = 7.7, 4J = 1.8 Hz, Hc), 7.64 (d, 1H, 3J = 3.8
3
Hz, Hf), 7.52 (d, 2H, J = 8.7 Hz, Hh), 7.49−7.41 (m, 2H, Hp, Hq),
7.33 (ddd, 1H, 3J = 7.5, 3J = 4.8, 4J = 1.1 Hz, Hb), 7.28 (t, 4H, 3J = 7.9
4-(5-(6-(3-Ethoxyphenyl)-2,2′-bipyridin-4-yl)thiophen-2-yl)-N,N-
diphenylaniline (L1H). P6 (498 mg, 1.14 mmol) and N,N-diphenyl-4-
(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (P8) (470 mg,
1.27 mmol) were solubilized in a THF/H2O (9:1, 125 mL) solution
and sparged with N2 for 10 min. To this solution were then added
K2CO3 (875 mg, 6.33 mmol) and Pd(PPh3)4 (102 mg, 0.09 mmol),
and the reaction mixture was set to reflux for 14 h under N2. The
reaction mixture was cooled to room temperature and then poured into
water. The product was extracted with Et2O and washed with brine.
Organic fractions were combined and dried with MgSO4, filtered, and
concentrated by removing the solvent in vacuo. The product was
purified by column chromatography [SiO2: CH2Cl2/EtOAc, 19:1; Rf =
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Hz, Hk), 7.26 (d, 1H, J = 4.3 Hz, Hg), 7.14 (d, 4H, J = 7.5 Hz, Hj),
7.09 (d, 2H, 3J = 8.6 Hz, Hi), 7.06 (t, 2H, 3J = 7.4 Hz, Hl), 3.05 (q, 2H,
3J = 7.3 Hz, −SCH2CH3), 1.38 (t, 3H, J = 7.3 Hz, −SCH2CH3); 13C
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NMR (CDCl3) δ 156.9, 156.5, 156.2, 149.2, 148.0, 147.5, 146.2, 143.4,
140.2, 139.8, 137.4, 137.1, 129.8, 129.6, 129.4, 128.0, 127.8, 126.9,
126.8, 125.0, 124.9, 124.8, 124.1, 123.5, 123.4, 121.7, 116.4, 115.5,
28.1, 14.6. HRMS (EI): m/z 617.1951 [(M)+] (calcd for C40H31N3S2
+
m/z 617.1959).
4-(5-(6-(3-(Ethylthio)phenyl)-2,2′-bipyridin-4-yl)thiophen-2-yl)-
N,N-bis(4-methoxyphenyl)aniline (L4H). P7 (475 mg, 1.05 mmol)
and P9 (502 mg, 1.16 mmol) were solubilized in a THF/water
solution (125 mL, 9:1 v/v) and sparged with N2 for 10 min. Following
the addition of K2CO3 (801 mg, 5.80 mmol) and Pd(PPh3)4 (102 mg,
0.09 mmol), the reaction mixture was left to reflux overnight under an
inert atmosphere. After the reaction mixture was cooled to room
temperature it was poured into H2O. The product was extracted with
Et2O (2 × 100 mL) and washed with brine (2 × 100 mL). The organic
fraction was dried with MgSO4 prior to the removal of the solvent
in vacuo. The resulting oil was purified by column chromatography
[SiO2: CH2Cl2/EtOAc (9:1); Rf = 0.91] to yield 335 mg (47.4%) of
the product as a bright yellow solid. 1H NMR (CDCl3): δ 8.70 (d, 1H,
1
0.49] to yield 468 mg (68.3%) of the product as a yellow solid. H
NMR (CDCl3): δ 8.72 (dd, 1H, 3J = 4.7, 4J = 0.8 Hz, Ha), 8.64 (d, 1H,
3J = 8.0 Hz, Hd), 8.60 (d, 1H, 4J = 1.6 Hz, He), 7.89 (d, 1H, 4J = 1.6 Hz,
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Hm), 7.84 (td, 1H, J = 7.6, J = 1.8 Hz, Hc), 7.76 (t, 1H, J = 1.4 Hz,
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Hr), 7.73 (d, 1H, J = 7.8 Hz, Hn), 7.63 (d, 1H, J = 3.9 Hz, Hf), 7.51
(d, 2H, 3J = 8.7 Hz, Hh), 7.42 (t, 1H, 3J = 7.9 Hz, Ho), 7.32 (ddd, 1H,
3J = 7.6 Hz, 3J = 4.8 Hz, 4J = 1.8 Hz, Hb), 7.30−7.25 (m, 5H, Hk, Hg),
7.13 (d, 4H, 3J = 8.3 Hz, Hj), 7.10−7.03 (m, 4H, Hi, Hl), 6.99 (dd, 1H,
3J = 7.5, 4J = 1.8 Hz, Hp), 4.16 (q, 2H, 3J = 7.0 Hz, −OCH2CH3), 1.48
(t, 3H, 3J = 7.0 Hz, −OCH2CH3). 13C NMR (CDCl3): δ 159.6, 157.2,
156.4, 156.3 149.2, 148.0, 147.5, 146.1, 143.3, 141.0, 139.9. 137.0,
129.9, 129.6, 127.9, 126.8, 126.7, 124.9, 124.1, 123.5, 123.5, 123.4,
121.7, 119.6, 116.5, 115.4, 115.2, 113.7, 63.8, 15.1. HRMS (EI): m/z
601.2162 [(M)+] (calcd for C40H31N3OS+ m/z 601.2188).
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3J = 4.3 Hz, Ha), 8.62 (d, 1H, J = 8.0 Hz, Hd), 8.59 (s, 1H, He), 8.16
(s, 1H, Hr), 7.94 (m, 1H, Hn), 7.86 (s, 1H, Hm), 7.82 (dt, 1H, 3J = 7.8
Hz, 4J = 1.6 Hz, Hc), 7.59 (d, 1H, 3J = 3.8 Hz, Hf), 7.46−7.38 (m, 4H,
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Hh, Hp, Ho), 7.31 (t, 1H, J = 6.7 Hz, Hb), 7.20 (d, 1H, J = 3.8 Hz,
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Hg), 7.08 (d, 4H, J = 8.9 Hz, Hj), 6.92 (d, 2H, J = 8.0 Hz, Hi), 6.85
4-(5-(6-(3-Ethoxyphenyl)-2,2′-bipyridin-4-yl)thiophen-2-yl)-N,N-
bis(4-methoyphenyl)aniline (L2H). 4-Methoxy-N-(4-methoxyphen-
yl)-N-(4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline
(P9) (510 mg, 1.18 mmol) and P6 (465 mg, 1.06 mmol) were
solubilized in a 9:1 THF/H2O (125 mL) solution and degassed for 10
min by sparging with N2. K2CO3 (820 mg, 5.91 mmol) and Pd(PPh3)4
(100 mg, 0.09 mmol) were then added, and the reaction mixture was
refluxed under N2 overnight. The reaction was then cooled to room
temperature and poured into H2O, and the product extracted with
Et2O. After the Et2O layer was washed with brine, the organic fractions
were collected and dried with MgSO4. The solvent was removed
in vacuo after filtration to yield an oil, which was solubilized in CH2Cl2
and preabsorbed on silica. The sample was purified by column
chromatography [SiO2: CH2Cl2/EtOAc, 9:1; Rf = 0.66] to yield 480
mg (68.2%) of the product as a bright yellow solid. 1H NMR (CDCl3):
δ 8.71 (d, 1H, 3J = 4.6 Hz, Ha), 8.63 (d, 1H, 3J = 7.9 Hz, Hd), 8.58 (d,
1H, 4J = 1.5 Hz, He), 7.89 (d, 1H, 4J = 1.5, Hm), 7.83 (td, 1H, 3J = 7.7,
4J = 1.7 Hz, Hc), 7.75 (s, 1H, Hr), 7.72 (d, 1H, 3J = 7.8 Hz, Hn), 7.62 (d,
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(d, 4H, J = 8.9 Hz, Hk), 3.79 (s, 6H, −OCH3), 3.04 (q, 2H, J = 7.3
Hz, −SCH2CH3), 1.38 (t, 3H, J = 7.3 Hz, −SCH2CH3). 13C NMR
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(CDCl3): δ 156.4, 156.2, 156.1, 156.0, 149.0, 148.7, 146.4, 143.1,
140.4, 139.9, 138.9, 137.3, 136.8, 129.4, 129.2, 127.6, 126.8, 126.7,
126.4, 125.6, 124.6, 123.9, 122.7, 121.4, 120.1, 116.0, 115.2, 114.8,
55.5, 27.8, 14.5. HRMS (EI): m/z 677.2187 [(M)+] (calcd for
+
C42H35N3O2S2 m/z 677.2171).
[Ru(P7)(L5)]NO3 (P10). To a suspension of P7 (553 mg, 1.22
mmol) in MeOH/H2O/THF (5:1:1, 210 mL) were added Ru(L5)Cl3
(750 mg, 1.22 mmol) and N-ethylmorpholine (0.5 mL). After the
reaction mixture was left to reflux overnight under an N2 atmosphere,
AgNO3 (622 mg, 3.66 mmol) was added followed by an additional 2 h
reflux. The hot solution was filtered, and then the solvent was removed
in vacuo. Purification of the solid by column chromatography [SiO2:
CH2Cl2/MeOH (9:1); Rf = 0.48] yielded 635 mg (50.9%) of the
product as a black powder. Low yields were attributed to the difficulty
of separating the ortho and para isomeric products; e.g., ortho/para 3:1
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1H, 3J = 3.8 Hz, Hf), 7.45 (d, 2H, 3J = 8.8 Hz, Hh), 7.41 (t, 1H, 3J = 7.9
Hz, Ho), 7.32 (dd, 1H, 3J = 4.9, 4J = 1.0 Hz, Hb), 7.21 (d, 1H, 3J = 3.8
as determined by H NMR spectroscopy. H NMR (CDCl3): δ 9.10
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(s, 2H, HE), 8.94 (d, 1H, J = 7.2 Hz, Hd), 8.92 (s, 1H, He), 8.86 (s,
2H, HD), 8.22 (s, 1H, Hm), 8.05 (d, 1H, 3J = 3.9 Hz, Hf), 7.84 (td, 1H,
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Hz, Hg), 7.08 (d, 4H, J = 8.3 Hz, Hj), 6.98 (dd, 1H, J = 8.1, 4J = 1.9
3J = 7.8, J = 1.2 Hz, Hc), 7.70 (d, 1H, J = 7.9 Hz, Hn), 7.68 (d, 2H,
3J = 5.9 Hz, HA), 7.65 (dd, 2H, 3J = 5.9, 4J = 1.4 Hz, HB), 7.25 (d, 1H,
3J = 3.5 Hz, Hg), 6.99 (t, 1H, 3J = 6.4 Hz, Hb), 6.88 (t, 1H, 3J = 7.8 Hz,
Ho), 6.56 (d, 1H, 3J = 5.3 Hz, Ha), 6.37 (d, 1H, 3J = 7.7 Hz, Hp), 4.20
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Hz, Hp), 6.92 (d, 2H, J = 8.7 Hz, Hi), 6.83 (d, 4H, J = 8.3 Hz, Hk),
4.16 (q, 2H, 3J = 7.2 Hz, −OCH2CH3), 3.79 (s, 6H, −OCH3), 1.47 (t,
3H, J = 7.2 Hz, −OCH2CH3). 13C NMR (CDCl3): δ 159.6, 157.3,
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156.4, 156.3, 156.2, 149.2, 148.9, 146.6, 143.4, 141.0, 140.7, 139.4,
137.1, 129.9, 127.0, 126.7, 125.9, 124.0, 122.9, 121.7, 120.4, 119.6,
116.5, 115.4, 115.2, 115.0, 113.7, 63.8, 55.7, 15.1. HRMS (EI): m/z
661.2383 [(M)+] (calcd for C42H35N3O3S+ m/z 661.2399).
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(s, 3H, HF), 3.94 (s, 6H, HC), 2.14 (q, 2H, J = 7.3 Hz, −SCH2CH3),
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0.68 (t, 3H, J = 7.3 Hz, −SCH2CH3); HRMS (ESI): m/z 954.0112
[(M)+] (calcd for C43H33BrN5O6RuS2 m/z 954.0126). Anal. Calcd
+
for C43H33BrN6O9RuS2·2H2O: C, 48.77; H, 3.52; N, 7.94. Found: C,
48.87; H, 3.34; N, 7.75.
4-(5-(6-(3-(Ethylthio)phenyl)-2,2′-bipyridin-4-yl)thiophen-2-yl)-
N,N-diphenylaniline (L3H). After a solution of P7 (549 mg, 1.21
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dx.doi.org/10.1021/om200784j|Organometallics 2011, 30, 6628−6635