Organometallics
Article
8
1
.4 Hz, 2H; aromatic protons), 4.53 (d, 2JHH = 15.4, 3JHH = 3.9 Hz,
MeOH (2 mL) and dried under vacuum, affording 16 (278 mg, 78%
+
H; NCH ), 4.12 (m, 1H; NH ), 3.91 (m, 1H; NCH ), 2.98 (m, 1H;
yield). HRMS: found [M − Cl] 735.1638, calcd for C H N P Ru
2
2
2
42 39
2 2
1
CH ), 2.64 (m, 1H; CH ), 2.48−1.25 (m, 5H, CH and NH2).
735.1627. H NMR (200.1 MHz, CD Cl ): δ 8.01 (m, 1H; aromatic
2
2
2
2 2
1
3
1
2
C{ H} NMR (50.3 MHz, CD Cl ): δ 178.1 (dd, J = 15.0, 9.4 Hz;
proton), 7.96−7.80 (m, 4H; aromatic protons), 7.63−6.89 (m, 16H;
2
2
CP
3
CRu), 155.2 (s; NCC), 152.2 (s; NCCH ), 146.5−117.1 (m, aromatic
carbons), 52.0 (d, J = 2.0 Hz, CH N), 29.9 (dd, J = 26.6, J =
2
aromatic protons), 6.49 (t, JHH = 6.8 Hz, 1H; aromatic proton), 6.18
2
3
3
3
1
3
(
td, J = 1.8, 7.7 Hz, 2H; aromatic protons), 5.72 (t, J = 8.2 Hz,
HH HH
CP
2
CP
CP
1
3
2
H; aromatic protons), 4.44 (m, 1H; NCH ), 4.18−3.67 (m, 2H;
.7 Hz, CH P), 24.9 (dd, J = 35.5 Hz, J = 3.4 Hz, CH P), 21.0
2
2
CP
CP
2
31
1
2
NCH and NH ), 2.91 (m, 1H; PCH ), 2.74−1.15 (m, 6H; CH and
NH ), 2.61 (s, 3H; CH ). C{ H} NMR (50.3 MHz, CD Cl ): δ
1
NCCH ), 146.3−117.6 (m, aromatic carbons), 51.8 (d, J = 2.2 Hz,
NCH ), 29.9 (dd, J = 26.6, J = 1.9 Hz; PCH ), 24.9 (dd, J =
(
s, CH CH P). P{ H} NMR (81.0 MHz, CD Cl ): δ 54.7 (d, J =
2
2
2
2
2
2
2
2
PP
13
1
2
4
8.6 Hz), 35.7 (d, JPP = 48.6 Hz). Anal. Calcd for C H ClN P Ru:
2
3
2
2
47
41
2 2
2
77.6 (dd, J = 14.9, 9.9 Hz; CRu), 155.1 (s; NCC), 151.2 (s;
C, 67.82; H, 4.97; N, 3.37. Found: C, 67.70; H, 4.71; N, 3.62.
CP
3
Ph
Synthesis of RuCl(CNN )(dppb) (14). RuCl (PPh ) (2.22 g,
2
CP
2
3 3
1
3
1
2
.32 mmol) and dppb (1.04 g, 2.44 mmol) were suspended in
2
CP
CP
2
CP
3
3
5.3, J = 3.1 Hz; PCH ), 21.0 (s, PCH CH ), 18.6 (s; CH ).
anhydrous 2-propanol (40 mL), and the mixture was refluxed under Ar
in a 250 mL round-bottom flask for 1.5 h. Compound 6 (820 mg, 2.56
mmol) and NEt (3.2 mL, 23 mmol) were added, and the mixture was
refluxed for 1.5 h. The suspension was cooled to room temperature,
and the bright orange precipitate was filtered, washed with MeOH (10
mL) and n-heptane (3 × 10 mL), and dried under reduced pressure,
CP 2 2 2 3
31
1
2
P{ H} NMR (81.0 MHz, CD Cl ): δ 55.0 (d, J = 48.4 Hz), 36.0
2
2
PP
2
(d, J = 48.4 Hz). Anal. Calcd for C H ClN P Ru: C, 65.49; H,
PP 42 39 2 2
3
5
.10; N, 3.64. Found: C, 65.01; H, 4.85; N, 3.51.
Synthesis of RuCl(CNN )(dppb) (17). The preparation of 17
Me
was carried out as described for complex 16, but using dppb (237 mg,
+
0.56 mmol, 1.2 equiv) in place of dppp, affording 17 (300 mg, 83%
affording 14 (1.68 g, 85% yield). HRMS: found [M − Cl] 811.1943,
calcd for C H N P Ru 811.1940. H NMR (200.1 MHz, CD Cl ): δ
+
1
yield). HRMS: found [M − Cl] 749.1788, calcd for C H N P Ru
43 41
2 2
48
43
2
2
2
2
749.1783. 1H NMR (400 MHz, CDCl ): δ 8.27−8.13 (m, 2H;
aromatic protons), 7.97 (d, J = 7.0 Hz, 1H; aromatic proton), 7.81
3
3
8
.23 (pseudo t, JHH = 7.6 Hz, 2H; aromatic protons), 8.03 (d, J
=
3
HH
3
3
4
7
.0 Hz, 1H; aromatic proton), 7.84 (td, J = 8.2, J = 1.3 Hz, 2H;
HH
HH
HH
3
3
3
(pseudo t, J = 8.2 Hz, 2H; aromatic protons), 7.66 (d, J = 8.9
aromatic protons), 7.61 (d, J = 9.0 Hz, 1H; H-5 benzoquinoline),
HH HH
HH
Hz, 1H; H-6 benzoquinoline), 7.55−7.22 (m, 14H; aromatic protons),
7
.54−7.25 (m, 19H; aromatic protons), 6.95 (s, 1H; H-3 benzoquino-
3
3 4
6.84 (s, 1H; H-3 benzoquinoline), 6.45 (pseudo t, J = 7.4 Hz, 1H;
line), 6.56 (td, J = 7.4, J = 1.3 Hz, 1H; aromatic proton), 6.23
HH
HH
HH
3
3
4
3
aromatic proton), 6.14 (pseudo t, JHH = 7.6 Hz, 2H; aromatic
(
td, J = 8.0, J = 2.0 Hz, 2H; aromatic protons), 5.54 (t, J
=
HH
HH
HH
3
2
2
3
protons), 5.74 (t, J = 8.2 Hz, 2H; aromatic protons), 4.33 (dd, J
HH HH
8
1
.1 Hz, 2H; aromatic protons), 4.41 (dd, JHH = 16.0, J = 5.4 Hz,
HH
3
=
15.9, J = 5.4 Hz, 1H; NCH ), 3.93 (m, 1H; NCH ), 3.61 (m, 1H,
HH 2 2
H; NCH ), 3.98 (m, 1H; NCH ), 3.69 (m, 1H; NH ), 2.96 (m, 2H;
2
2
2
NH ), 3.26−2.77 (m, 2H; CH ), 2.44−0.96 (m, 7H; CH and NH ),
2
2
2
2
CH ), 2.37 (m, 1H; CH ), 2.21−1.68 (m, 5H; CH and NH ), 1.15
2
2
2
2
13
1
13
1
2
2.52 (s, 3H; CH
3
). C{ H} NMR (50.3 MHz, CD
2
Cl
2
): δ 178.6 (dd,
(
m, 1H; CH ). C{ H} NMR (50.3 MHz, CD Cl ): δ 178.9 (dd, J
2 2 2 CP
2
JCP = 16.6, 8.2 Hz; CRu), 154.7 (s; NCC), 151.7 (s; NCCH ), 146.7−
117.5 (m, aromatic carbons), 52.3 (d, J = 2.6 Hz, NCH ), 33.2 (d,
JCP = 26.6 Hz; PCH ), 30.2 (d, J = 32.0 Hz; PCH ), 26.8 (s,
PCH CH ), 21.9 (s, PCH CH ), 18.4 (s; CH ). P{ H} NMR (81.0
2 2 2 2 3
2
=
16.5, 8.2 Hz; CRu), 154.8 (s; NCC), 152.7 (s; NCCH ), 146.6−
3
2
3
1
17.0 (m, aromatic carbons), 52.5 (d, J = 2.6 Hz, CH N), 33.3 (d,
CP
2
CP
2
1
1
1
1
2 CP 2
JCP = 24.9 Hz, CH P), 30.3 (d, J = 32.0 Hz, CH P), 26.9 (s,
2
CP
1
2
31
1
31
CH CH P), 22.0 (s, CH CH P). P{ H} NMR (81.0 MHz, CD Cl ):
δ 57.3 (d, J = 38.1 Hz), 43.3 (d, J = 38.1 Hz). Anal. Calcd for
C H ClN P Ru: C, 68.12; H, 5.12; N, 3.31. Found: C, 67.95; H,
2
2
2
2
2
2
2
2
2
2
MHz, CD Cl ): δ 57.7 (d, J = 38.0 Hz), 43.6 (d, J = 38.0 Hz).
2 2 PP PP
PP
PP
Anal. Calcd for C H ClN P Ru: C, 65.85; H, 5.27; N, 3.57. Found:
43
41
2 2
4
8
43
2 2
C, 65.59; H, 5.39; N, 3.50.
4
.91; N, 3.45.
Synthesis of RuCl(CNN )(dppf) (15). RuCl (PPh ) (2.22 g,
Synthesis of RuCl(CNNMe)(dppf) (18). The preparation of 18 was
carried out as described for complex 16, but using dppf (311 mg, 0.56
mmol, 1.2 equiv) in place of dppp, affording 18 (184 mg, 44% yield).
Ph
2
3 3
2
.32 mmol) and dppf (1.54 mg, 2.78 mmol) were suspended in 2-
propanol (20 mL), and the mixture was refluxed under Ar in a 250 mL
round-bottom flask for 1.5 h. Compound 6 (820 mg, 2.55 mmol) and
NEt (3.2 mL, 23 mmol) were added, and the mixture was refluxed for
+
HRMS: found [M − Cl] 877.1148, calcd for C H FeN P Ru
49
41
2 2
8
77.1132. 1H NMR (400 MHz, CDCl ): δ 8.62−8.44 (m, 3H;
aromatic protons), 8.10 (pseudo t,
3
3
3
J
= 8.5 Hz, 2H; aromatic
HH
5
h. The suspension was cooled to room temperature, and n-heptane
protons), 7.81−7.05 (m, 16H; aromatic protons), 6.94 (s, 1H; H-3
(
40 mL) was added. The orange precipitate was filtered, washed with
3
benzoquinoline), 6.53 (pseudo t, J = 7.1 Hz, 1H; aromatic proton),
HH
MeOH (10 mL) and n-heptane (3 × 10 mL), and dried under reduced
3
3
6
.22 (pseudo t, J = 6.9 Hz, 2H; aromatic protons), 5.99 (t, J
=
+
HH
HH
pressure, affording 15 (2.03 g, 90% yield). HRMS: found [M − Cl]
8
.5 Hz, 2H; aromatic protons), 5.25 (s, 1H, C H ), 4.83 (s, 1H,
1
5
4
9
39.1301, calcd for C H FeN P Ru 939.1289. H NMR (200.1
54
43
2 2
C H ), 4.40−4.05 (m, 5H; NCH and C H ), 3.86−3.57 (m, 3H; NH
5
4
2
5
4
MHz, CD Cl ): δ 8.61−8.49 (m, 3H; aromatic protons), 8.12 (pseudo
2
2
and C H ), 3.17 (s, 1H, C H ), 2.57 (s, 3H; CH ), 2.14 (m, 1H;
3
5
4
5
4
3
t, J = 8.1 Hz, 2H; aromatic protons), 7.84−7.09 (m, 21H; aromatic
13
1
2
HH
NH2). C{ H} NMR (50.3 MHz, CD Cl ): δ 176.0 (dd, J = 15.5,
5
2
2
CP
protons), 7.05 (d, J = 1.0 Hz, 1H, H-3 benzoquinoline), 6.63 (td,
HH
8
.7 Hz; CRu), 155.3 (s; NCC), 151.9 (s; NCCH ), 146.8−118.0 (m,
3
4
3
2
JHH = 7.2, J
= 1.3 Hz, 1H; aromatic proton), 6.31 (td, J = 7.9,
1 3
HH
HH
aromatic carbons), 87.8 (dd, J = 39.4, J = 4.1 Hz; PCC H ), 86.3
(dd, J = 50.7, J = 2.4 Hz; PCC H ), 77.8−69.0 (m, CH of
C H ), 51.6 (d, J = 2.1 Hz, NCH ), 18.5 (s; CH ). P{ H} NMR
CP
CP
4
4
4J
= 2.1 Hz, 2H; aromatic protons), 6.08 (pseudo t, J = 8.3 Hz,
3
1
3
HH
HH
CP
CP
4
4
2
H; aromatic protons), 5.28 (m, 1H; C H ), 4.84 (m, 1H; C H ),
3 31 1
5 4 CP 2 3
5
4
5
4
2
2
4
.48−4.09 (m, 5H; CH and C H ), 3.91−3.67 (m, 3H; C H and
2
5
4
5
4
(81.0 MHz, CD Cl ): δ 62.3 (d, J = 36.0 Hz), 45.5 (d, J = 36.0
2 2 PP PP
13
1
NH), 3.20 (m, 1H; C H ), 2.24 (m, 1H; NH ). C{ H} NMR (50.3
MHz, CD Cl ): δ 176.4 (dd, J = 15.5, 8.8 Hz; CRu), 155.4 (s;
5
4
2
Hz). Anal. Calcd for C H ClFeN P Ru: C, 64.52; H, 4.53; N, 3.07.
49 41 2 2
2
2
2
CP
Found: C, 64.38; H, 4.69; N, 2.89.
Ph
NCC), 152.9 (s; NCCH ), 147.0−117.4 (m, aromatic carbons), 87.6
2
Synthesis of RuCl(CNN )(rac-BINAP) (19). [RuCl (p-cymene)]
2 2
1
3
1
3
(
dd, J = 39.6, J = 4.2 Hz; PCC H ), 86.2 (dd, J = 50.9, J =
(71 mg, 0.116 mmol) and rac-BINAP (152 mg, 0.244 mmol) were
suspended in 2-propanol (2 mL), and the mixture was refluxed in a 25
mL round-bottom flask for 2 h. Compound 6 (82 mg, 0.256 mmol)
CP
CP
4
4
CP
CP
3
2
.5 Hz; PCC H ), 77.8−69.0 (m, CH of C H ), 51.7 (d, J = 2.1 Hz,
4
4
5
4
CP
3
1
1
2
NCH ). P{ H} NMR (81.0 MHz, CD Cl ): δ 62.0 (d, J = 36.0
Hz), 45.2 (d, J = 36.0 Hz). Anal. Calcd for C H ClFeN P Ru: C,
2
2
2
PP
2
PP
54 43
2
2
and NEt (0.32 mL, 2.3 mmol) were added, and the mixture was
3
6
6.57; H, 4.45; N, 2.88. Found: C, 66.81; H, 4.73; N, 2.67.
Synthesis of RuCl(CNNMe)(dppp) (16). In a 100 mL Schlenk
were introduced, under an Ar atmosphere, RuCl (PPh ) (445 mg,
refluxed for 6 h. The mixture was cooled to room temperature, and n-
heptane (4 mL) was added. The precipitate was filtered, washed with
MeOH (1 mL) and diethyl ether (5 × 2 mL), and dried under reduced
pressure, obtaining complex 19 as a mixture of two stereoisomers in+
about 4/3 molar ratio (150 mg, 62% yield). HRMS: found [M − Cl]
2
3 3
0
.46 mmol), dppp (199 mg, 0.48 mmol), and 2-propanol (10 mL).
The reaction mixture was refluxed for 1 h, 12 (131 mg, 0.506 mmol)
and triethylamine (0.64 mL, 4.6 mmol) were added, and the reaction
mixture was refluxed overnight. The reaction mixture was cooled to
RT, and the solid was filtered off. The precipitate was washed with
1
1007.2254, calcd for C H N P Ru 1007.2258. H NMR (200.1
64
47
2 2
3
MHz, CD Cl ): δ 8.59 (d, J = 6.4 Hz; aromatic protons), 8.40−
8.13 (m; aromatic protons), 8.02−6.22 (m; aromatic protons), 6.13−
2
2
HH
I
Organometallics XXXX, XXX, XXX−XXX