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imeter (1 s response, 3.41 nm bandwidth, scanning speed of
7.19 (t, 1 H), 7.08 (m, 2 H), 6.73 (d, 2 H), 6.57 (d, 2 H), 4.63 (s, 1
H), 3.23 (d, 1 H), 2.90 (d, 1 H) ppm. C NMR (75.5 MHz,
–1
13
200 nmmin , accumulation of three scans). The enantiomeric ex-
cess (ee) values of the ruthenium complexes and sulfoxide com-
pounds were determined by 1H NMR with use of (S)-1,1Ј-bi-
naphthol (S-Binol) and l-phenylglycinol, respectively, as chiral
shift reagents.
3
CD CN): δ = 177.7, 159.2, 158.6, 158.3, 158.1, 153.8, 153.2, 151.5,
150.9, 138.5, 138.2, 138.0, 137.9, 137.4, 135.9, 134.6, 133.8, 130.4,
130.4, 129.9, 129.9, 129.5, 129.5, 128.4, 128.1, 128.1, 128.1, 127.2,
126.7, 124.7, 124.4, 124.1, 124.0, 55.4, 37.2 ppm. ESI-MS: m/z =
+
739 [M – PF
6
] . C35
H
27Cl
2
F
6
N
4
O
2
PRuS (884.6): calcd. C 47.52, H
General Procedure for the Preparation of the Thioether Complexes:
The appropriate ruthenium complex (0.5 mmol), the appropriate
thioether ligand (1.0 mmol), K CO (0.25 mmol), and ethylene
2 3
glycol (2 mL) were placed in a three-necked flask. The mixture was
magnetically stirred and heated at 110 °C for 1 h under argon. The
reaction mixture was allowed to cool to room temperature, and
the crude material was purified by silica gel chromatography with
3
.08, N 6.33, S 3.62; found C 47.22, H 3.14, N 6.24, S 3.53. Λ-
(OSdpCl)](PF ) (Λ-3), yield 92% {Λ-[Ru(bpy) (MeCN) ]-
was used as the precursor}, ee 98%. CD (Δε/m cm ,
[Ru(bpy)
2
6
2
2
–1
–
1
(
PF
6
)
2
MeCN): 283 (–66), 296 (+181), 345 nm (+18). Δ-[Ru(bpy)
OSdpCl)](PF ) (Δ-3), yield 92% {Δ-[Ru(bpy) (MeCN) ](PF was
used as the precursor}, ee 98%. CD (Δε/m cm , MeCN): 283
+68), 297 (–176), 345 nm (–19).
2
-
(
6
2
2
6 2
)
–
1
–1
(
MeCN, MeCN/H
(
(
2
O (10:1, v/v), and finally CH
sat) (100:1:0.2, v/v/v) as eluents. After removal of the solvent, water General Procedure for the Asymmetric Oxidation of Sulfoxide Com-
20 mL) was used to dissolve the resulting product, and an excess plexes: A solution of the appropriate ruthenium thioether complex
was added to the solution. Then, CH Cl (15 mL) (0.05 mmol) and m-CPBA (0.075 mmol) in CH Cl (2 mL) was
was added to the solution, and the layers were separated. The aque-
ous phase was extracted with CH Cl (2ϫ 10 mL), and the com-
, filtered, concentrated,
3 2 3
CN/H O/KNO
of solid KPF
6
2
2
2
2
stirred for 5 h at room temperature, and then ether was added to
induce precipitation. The solid was isolated by vacuum filtration,
rinsed with ether, and air-dried.
2
2
bined organic phase was dried with MgSO
and dried under high vacuum.
4
[
Ru(bpy)
2
(4)](PF
6
) (rac-1a): Yield 94% (rac-1 was used as the start-
CN): δ = 10.24 (d, 1 H),
1
[
Ru(bpy)
2
(OSdp)](PF
6
) (rac-1): Yield 90%. [cis-Ru(bpy)
O (2 mL) were
used as solvent at 90 °C for 2.5 h]. H NMR (300.1 MHz, CD CN):
2
Cl
2
·2H
2
O
ing material). H NMR (300.1 MHz, CD
3
was used as the precursor, EtOH (18 mL) and H
2
8.96 (d, 1 H), 8.46 (d, 1 H), 8.38 (d, 1 H), 8.17 (t, 1 H), 8.10 (t, 1
H), 7.98 (m, 2 H), 7.90 (d, 1 H), 7.82 (m, 2 H), 7.74 (m, 2 H), 7.45
1
3
δ = 9.55 (d, 1 H), 9.18 (d, 1 H), 8.43 (d, 1 H), 8.32 (d, 1 H), 8.11 (m, 2 H), 7.36 (m, 3 H), 7.25 (m, 2 H), 7.01 (t, 1 H), 6.82 (d, 1 H),
1
3
(
7
m, 2 H), 7.86 (m, 5 H), 7.65 (d, 1 H), 7.55 (t, 1 H), 7.41 (d, 2 H),
6.72 (m, 4 H), 4.84 (s, 1 H), 4.23 (d, 1 H), 3.68 (d, 1 H) ppm.
NMR (75.5 MHz, CD CN): δ = 173.6, 158.6, 158.1, 157.9, 156.8,
H), 4.68 (s, 1 H), 3.22 (d, 1 H), 2.85 (d, 1 H) ppm. C NMR 156.3, 153.3, 151.8, 149.7, 139.9, 139.5, 139.1, 137.7, 137.6, 133.9,
C
.25 (m, 4 H), 7.08 (m, 2 H), 6.94 (t, 1 H), 6.72 (t, 2 H), 6.56 (d, 2
3
13
(
75.5 MHz, CD
3
CN): δ = 178.1, 159.2, 158.6, 158.3, 158.1, 153.5, 131.6, 131.6, 129.8, 129.8, 129.6, 129.2, 129.2, 128.7, 128.6, 128.2,
127.6, 127.1, 127.0, 127.0, 124.9, 124.9, 124.8, 124.1, 73.5,
1
1
1
53.3, 151.2, 150.8, 140.2, 139.0, 138.0, 137.8, 137.7, 136.0, 129.7,
29.7, 129.5, 129.5, 129.0, 128.8, 128.8, 128.2, 128.2, 128.1, 127.0,
26.4, 126.1, 126.1, 124.6, 124.3, 124.2, 124.0, 56.9, 37.2 ppm. ESI-
+
61.5 ppm. ESI-MS: m/z = 687 [M – PF
(831.7): calcd. C 50.54, H 3.51, N 6.74, S 3.86; found C 50.38, H
{(S)-4}](PF ) (Λ-1a), yield 94%
6 29 6 4 3
] . C35H F N O PRuS
+
MS: m/z = 671 [M – PF
6
] . C35
H
29
F
6
N
4
O
2
PRuS (815.73): calcd. C 3.77, N 6.79, S 3.74. Λ-[Ru(bpy)
2
6
–
1
–1
5
1.53, H 3.58, N 6.87, S 3.93; found C 51.31, H 3.72, N 6.79, S (Λ-1 was used as the starting material), de 98%. CD (Δε/m cm ,
.80. Λ-[Ru(bpy) (OSdp)](PF ) (Λ-1), yield 93% {Λ-[Ru(bpy) MeCN): 274 (–45), 290 (+90), 392 (–11), 448 nm (+14). Δ-
](PF was used as the precursor}, ee 98%. CD (Δε/ [Ru(bpy) {(R)-4}](PF ) (Δ-1a), yield 94% (Δ-1 was used as the
cm , MeCN):283 (–96), 296 (+201), 346 nm(+23). Δ-[Ru(bpy) starting material), de 98%. CD (Δε/m cm , MeCN): 274 (+45),
) (Δ-1), yield 93% {Δ-[Ru(bpy) (MeCN) ](PF was 290 (–88), 392 (+11), 448 nm (–13).
used as the precursor}, ee 98%. CD (Δε/m cm , MeCN): 283
+94), 297 (–199), 346 nm (–24).
3
(
m
2
6
2
-
MeCN)
2
6
)
2
2
6
–1
–1
–1
–1
2
-
(
OSdp)](PF
6
2
–
2
6 2
)
1
–1
[
Ru(bpy)
2
(5)](PF
6
) (rac-2a): Yield 95% (rac-2 was used as the start-
CN): δ = 10.21 (d, 1 H),
(
1
ing material). H NMR (300.1 MHz, CD
3
[
Ru(bpy) (OSdpF)](PF ) (rac-2): Yield 92% (the procedures were
2
6
8.94 (d, 1 H), 8.45 (d, 1 H), 8.38 (d, 1 H), 8.17 (t, 2 H), 8.00 (m, 3
1
similar to those used for rac-1). H NMR (300.1 MHz, CD
3
CN): H), 7.82 (m, 4 H), 7.46 (m, 2 H), 7.26 (m, 2 H), 7.11 (t, 2 H), 6.80
δ = 9.56 (d, 1 H), 9.17 (d, 1 H), 8.43 (d, 1 H), 8.32 (d, 1 H), 8.13 (m, 3 H), 6.48 (t, 2 H), 4.85 (s, 1 H), 4.18 (d, 1 H), 3.68 (d, 1
1
3
(
t, 2 H), 8.05 (d, 1 H), 7.83 (m, 5 H), 7.60 (t, 1 H), 7.43 (m, 2 H), H) ppm. C NMR (75.5 MHz, CD
3
CN): δ = 173.6, 164.9, 163.6,
7
.19 (t, 1 H), 7.07 (m, 4 H), 6.60 (m, 2 H), 6.48 (t, 2 H), 4.66 (s, 1 162.4, 161.1, 158.5, 158.0, 157.9, 156.8, 156.2, 153.5, 152.1, 149.7,
13
H), 3.23 (d, 1 H), 2.86 (d, 1 H) ppm. C NMR (75.5 MHz, 140.0, 139.8, 139.2, 137.8, 133.6, 133.5, 129.3, 129.2, 128.9,
CD CN): δ = 177.8, 164.2, 163.5, 161.8, 161.0, 159.2, 158.6, 158.3, 128.6, 127.7, 127.3, 124.9, 124.7, 124.5, 124.2, 116.6, 116.4,
3
+
1
1
1
7
3
58.0, 153.7, 153.2, 151.4, 150.8, 138.2, 137.9, 137.8, 136.0, 130.8,
30.8, 128.4, 128.3, 128.2, 128.1, 127.1, 126.6, 124.7, 124.3, 124.1,
24.0, 116.7, 116.4, 116.3, 116.1, 55.2, 37.3 ppm. ESI-MS: m/z =
07 [M – PF
.20, N 6.58, S 3.76; found C 49.50, H 3.32, N 6.51, S 3.73. Λ-
(OSdpF)](PF ) (Λ-2), yield 92% {Λ-[Ru(bpy) (MeCN) ]- (+8). Δ-[Ru(bpy)
was used as the precursor}, ee 98%. CD (Δε/m cm ,
116.2, 116.0, 71.7, 61.6 ppm. ESI-MS: m/z = 723 [M – PF
PRuS (867.7): calcd. C 48.45, H 3.14, N 6.46, S 3.70;
found C 48.38, H 3.27, N 6.33, S 3.64. Λ-[Ru(bpy) {(S)-5}](PF
(Λ-2a), yield 95% (Λ-2 was used as the starting material), de 98%.
6
] .
35 27 8 4 3
C H F N O
2
6
)
+
6
] . C35
H
27
F
8
N
4
O
2
PRuS (851.7): calcd. C 49.36, H
–
1
–1
CD (Δε/m cm , MeCN): 275 (–36), 292 (+75), 393 (–90), 448 nm
[Ru(bpy)
2
6
2
2
–1
2
{(R)-5}](PF ) (Δ-2a), yield 95% (Δ-2 was used as
the starting material), de 98%. CD (Δε/m cm , MeCN): 276
6
–
1
–1
–1
(PF
6
)
2
MeCN): 283 (–75), 297 (+175), 345 nm (+20). Δ-[Ru(bpy)
OSdpF)](PF ) (Δ-2), yield 92% {Δ-[Ru(bpy) (MeCN) ](PF was
used as the precursor}, ee 98%. CD (Δε/m cm , MeCN): 283
+70), 297 (–160), 345 nm (–19).
2
-
(+35), 292 (–77), 393 (+9), 448 nm (–7).
(
6
2
–
2
6 2
)
[
Ru(bpy)
ing material). H NMR (300.1 MHz, CD
.93 (d, 1 H), 8.45 (d, 1 H), 8.38 (d, 1 H), 8.18 (t, 2 H), 7.99 (m, 3
2
(6)](PF
6
) (rac-3a): Yield 93% (rac-3 was used as the start-
1
–1
1
3
CN): δ = 10.21 (d, 1 H),
(
8
[
Ru(bpy) (OSdpCl)](PF ) (rac-3): Yield 88% (the procedures were
2
6
H), 7.82 (m, 4 H), 7.41 (m, 4 H), 7.28 (m, 2 H), 6.81 (d, 1 H), 6.74
1
13
similar to those used for rac-1). H NMR (300.1 MHz, CD
3
CN): (m, 4 H), 4.83 (s, 1 H), 4.20 (d, 1 H), 3.66 (d, 1 H) ppm. C NMR
δ = 9.57 (d, 1 H), 9.16 (d, 1 H), 8.43 (d, 1 H), 8.32 (d, 1 H), 8.11 (75.5 MHz, CD
3
CN): δ = 173.3, 158.5, 158.0, 157.9, 156.7, 156.3,
(m, 3 H), 7.82 (m, 5 H), 7.62 (t, 1 H), 7.41 (d, 2 H), 7.33 (d, 2 H), 153.6, 152.1, 149.7, 140.0, 139.9, 139.2, 137.7, 135.9, 135.5, 134.1,
Eur. J. Inorg. Chem. 2015, 4335–4342
4340
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim