KOTZÉ AND MAPOLIE
11
3
3
vacuum. The product was isolated as a yellow powder in
moderate to high yields.
(d, J
= 8.2 Hz, 1H, Pyr), 8.27 (d, J
= 8.3 Hz, 1H,
H‐H
H‐H
3
3
Pyr), 8.65 (d, JH‐H = 8.5 Hz, 1H, Pyr), 8.85 (d, JH‐
= 8.2 Hz, 1H, Ar), 9.00 (s, 1H, CH‐imine). C { H}
NMR (75 MHz, (CD ) SO, δ, ppm): 11.3 (CH ); 21.1,
1
3
1
Model complex C1. Orange solid; yield 73%. FT‐IR (ν,
H
−
1
1
cm ): 1597 (s, imine, C═N), 734, 704 (s, B˙C). H NMR
3 2 3
3
(
3
(
300 MHz, (CD ) SO, δ, ppm): 0.94 (t, J
H, NCH CH CH ), 0.92 (d, JH‐H = 6.9 Hz, 3H, CH
CH3)2CYE), 1.01 (d, J
= 7.3 Hz,
21.9, 22.4 (CH3CYE); 18.4, 68.2 (CH ); 30.5, 83.7, 84.6,
3
2
H‐H
2
3
86.3, 87.0 (CHCYE); 104.7, 104.5 (CCYE), 123.5, 128.8,
130.0, 133.0, 140.7, 148.4, 155.6 (CHpyr); 155.2 (Cpyr);
167.9 (CH‐imine). Anal. Calcd for C H BClN Ru·H O,
2
2
3
3
= 6.8 Hz, 3H, CH(CH )
),
H‐H
3 2CYE
1
2
.83 and 1.95 (m, 2H, NCH CH CH ), 2.16 (s, 3H, CH3CYE),
2 2 3
47 48
2
2
.50 (sep, 1H, CH(CH3)2CYE, masked by DMSO signal), 4.23
CH Cl (890.23) (%): C, 64.69; H, 5.88; N, 3.14. Found
2 2
3
and 4.48 (m, 2H, NCH CH CH ), 5.91 (t, J = 5.2 Hz,
H‐H
(%): C, 64.96; H, 5.75; N, 2.93. MS (ESI, m/z): 469.1 [M]
. M.p. 216–219°C.
For siloxane‐functionalized complex C4, functionalized
ligand L4 (0.101 g, 0.326 mmol) was dissolved in DCM
(5.0 ml) and added dropwise to a stirred solution of [Ru(p‐
2
2
3
3
+
2
H, ArCYE), 6.17 (d, J
= 5.9 Hz, 1H, ArCYE), 6.24 (d,
H‐H
3
JH‐H = 6.3 Hz, 1H, Ar ), 6.79, 6.92, 7.19 (t, t, m, 20H,
CYE
3
3
B(Ph) ), 7.79 (t, J
= 6.0 Hz, 1H, Pyr), 8.14 (d, J
6.6 Hz, 1H, Pyr), 8.23 (t, J
= 5.4 Hz, 1H, Pyr), 8.73 (s, 1H, CH‐imine).
C { H} NMR (75 MHz, (CD ) SO, δ, ppm): 11.3 (CH );
4
H‐H
H‐
3
=
= 7.6 Hz, 1H, Pyr),
H
H‐H
3
9
.60 (d, J
cymene)Cl ] (0.100 g, 0.163 mmol) in DCM (10 ml). The
H‐H
2 2
1
3
1
solution was allowed to stir overnight at room temperature
under nitrogen atmosphere. The volume of the resulting solu-
tion was reduced to about half after the allotted time. NaB
3
2
3
2
8
1
1.3, 22.1, 22.4 (CH3CYE); 18.3, 67.7 (CH ); 30.4, 84.2,
4.8, 84.9, 87.2 (CHCYE); 103.0, 104.4 (CCYE), 128.2,
28.6, 139.7, 154.4, (CHpyr); 155.8 (Cpyr); 167.1 (CH‐
2
(Ph) (0.110 g, 0.326 mmol) was added and the reaction
4
imine). Anal. Calcd for C H BClN Ru (738.2) (%): C,
was stirred at 0°C for a further 3 h. The flask was left in a
freezer overnight to precipitate the product, which was fil-
tered, washed with ethanol and diethyl ether and dried under
vacuum. The product was isolated as a yellow powder in
moderate to high yields.
4
3
46
2
6
3
9.96; H, 6.28; N, 3.79. Found (%): C, 69.63; H, 6.28; N,
.49. MS (ESI, m/z): 419.1 [M] . M.p. 176–178°C.
+
Model complex C2. Light brown solid; yield 70%. FT‐IR
−1
1
(
ν, cm ): 1598 (s, imine, C═N), 735, 707 (s, B─C). H
3
NMR (300 MHz, (CD ) SO, δ, ppm): 0.89 (t, JH‐
Functionalized complex C4. Orange solid; yield 65%.
3
2
3
−1
=
7.3 Hz, 3H, NCH CH CH ), 0.89 (d, J = 7.3 Hz,
H‐H
FT‐IR (ν, cm ): 1596 (s, imine, C═N), 733, 705 (s, B─C).
H
2
2
3
3
1
3
3
H, CH(CH3)2CYE), 0.97 (d, J
= 7 Hz, 3H, CH(CH3)
H NMR (400 MHz, (CD ) SO, δ, ppm): 0.69 (t, JH‐
H‐H
3 2
3
CYE), 1.82 and 1.92 (m, 2H, NCH CH CH ), 2.17 (s, 3H,
= 7.3 Hz, 3H, NCH CH CH Si), 0.92 (d, JH‐
2
2
2
3
H
2
2
2
3
CH3CYE), 2.50 (sep, 1H, CH(CH3)2CYE, masked by DMSO
signal), 3.10 (s, 3H, CH Pyr), 4.22 and 4.45 (m, 2H,
= 6.9 Hz, 3H, CH(CH )
), 1.01 (d, J
= 6.8 Hz,
H‐H
= 8.0 Hz, 9H, CH CH Si
H‐H 2 2
H
3 2CYE
3
3H, CH(CH )
), 1.19 (t, J
3
3 2CYE
3
NCH CH CH ), 5.84 (d, J
= 6.2 Hz, 1H, ArCYE), 5.88
(OCH CH ) ), 1.83 and 1.95 (m, 2H, NCH CH CH Si),
2 3 3 2 2 2
2
2
3
H‐H
3
3
(
d, J
= 6.2 Hz, 1H, Ar ), 6.24 (d, J
= 5.9 Hz,
2.16 (s, 3H, CH3 CYE), 2.50 (sep, 1H, CH(CH )
, masked
H‐H
CYE
H‐H
3 2CYE
3
3
1
6
1
H, ArCYE), 6.33 (d, J
= 5.9 Hz, 1H, ArCYE), 6.79,
by DMSO signal), 3.84 (q, J = 6.9 Hz, 6H, CH CH Si
H‐H 2 2
H‐H
3
.92, 7.17 (t, t, m, 20H, B(Ph) ), 7.75 (d, J
= 6.5 Hz,
(OCH CH ) ), 4.23 and 4.48 (m, 2H, NCH CH CH Si),
2 3 3 2 2 2
4
H‐H
3
3
3
3
H, Pyr), 7.95 (d, J
= 7.3 Hz, 1H, Pyr), 8.09 (t, J
8.1 Hz, 1H, Pyr), 8.67 (s, 1H, CH‐imine). C { H}
5.91 (t, JH‐H = 5.2 Hz, 2H, ArCYE), 6.17 (d, JH‐
H‐H
H‐
1
3
1
3
=
= 5.9 Hz, 1H, ArCYE), 6.24 (d, J
6.79, 6.92, 7.19 (t, t, m, 20H, B(Ph) ), 7.79 (t, JH‐
4
= 6.0 Hz, 1H, Pyr), 8.14 (d, J
= 6.3 Hz, 1H, Ar ),
H
H
H‐H CYE
3
NMR (75 MHz, (CD ) SO, δ, ppm): 11.3 (CH ); 21.5,
3
2
3
3
2
8
2.1, 22.2 (CH3CYE); 18.5, 67.7 (CH ); 28.0 (PyrCH3) 30.5,
1.4, 83.7, 86.9, 89.8 (CHCYE); 126.6, 128.6, 139.1, 154.8
= 6.6 Hz, 1H, Pyr),
2
H
H‐H
3
3
8.23 (t, J
= 7.6 Hz, 1H, Pyr), 9.60 (d, J
= 5.4 Hz,
C { H} NMR
H‐H
H‐H
13
1
(
CHpyr); 155.2 (Cpyr); 167.6 (CH‐imine). Anal. Calcd for
1H, Pyr), 8.73 (s, 1H, CH‐imine).
C H BClN Ru (752.2) (%): C, 70.26; H, 6.43; N, 3.72.
(150 MHz, (CD ) SO, δ, ppm): 11.3 (CH ); 18.2, 57.8 (Si
4
4
48
2
3 2
3
Found (%): C, 69.93; H, 6.15; N, 3.38. MS (ESI, m/z):
(OCH CH ) ); 21.3, 22.1, 22.4 (CH3CYE); 18.3, 67.7 (CH2);
2 3 3
+
433.1 [M] . M.p. 206–209°C.
30.4, 84.2, 84.8, 84.9, 87.2 (CHCYE); 103.0, 104.4 (CCYE),
128.2, 128.6, 139.7, 154.4, (CHpyr); 155.8 (Cpyr); 167.1
(CH‐imine). Anal. Calcd for C H BClN O RuSi (900.4)
Model complex C3. Brown solid; yield 78%. FT‐IR (ν,
−
1
1
cm ): 1592 (s, imine, C═N), 732, 706 (s, B─C). H NMR
49
60
2 3
3
(
3
(
300 MHz, (CD ) SO, δ, ppm): 0.94 (t, J = 7.3 Hz,
H, NCH CH CH ), 0.73 (d, JH‐H = 6.7 Hz, 3H, CH
CH3)2CYE), 0.84 (d, JH‐H = 7 Hz, 3H, CH(CH )
(%): C, 65.36; H, 6.72; N, 3.11. Found (%): C, 64.97; H,
3
2
H‐H
3
+
6.12; N, 2.97. MS (ESI, m/z): 581.2 [M − B(Ph) ] . M.p.
2
2
3
4
3
),
decomposed without melting (140–145°C).
3 2CYE
1
2
.91 and 2.00 (m, 2H, NCH CH CH ), 2.15 (s, 3H, CH3CYE),
Functionalized complex C5. Light brown solid; yield
2
2
3
−
1
.50 (sep, 1H, CH(CH3)2CYE, masked by DMSO signal), 4.41
68%. FT‐IR (ν, cm ): 1597 (s, imine, C═N), 733, 705 (s,
3
1
and 4.62 (m, 2H, NCH CH CH ), 5.93 (d, J
= 6.2 Hz,
B─C). H NMR (400 MHz, (CD ) SO, δ, ppm): 0.61 (t,
2
2
3
H‐H
3 2
3
3
3
1
H, ArCYE), 6.11 (d, J
= 6.2 Hz, 1H,ArCYE), 6.23 (d,
JH‐H = 7.3 Hz, 3H, NCH CH CH Si), 0.91 (d, JH‐
= 7.3 Hz, 3H, CH(CH )
H‐H
2 2 2
3
3
3
JH‐H = 6.5 Hz, 1H, ArCYE), 6.34 (d, J
= 6.2 Hz, 1H,
), 0.97 (d, J
= 7 Hz, 3H,
H‐H
= 8.0 Hz, 9H, CH CH Si
H‐H 2 2
H‐H
H
3 2CYE
3
3
ArCYE), 6.78, 6.92, 7.18 (t, t, m, 20H, B(Ph) ), 7.98 (t, J
CH(CH )
), 1.16 (t, J
4
H‐
3 2CYE
3
=
8 Hz, 1H, Pyr), 8.13 (t, J
= 8.1 Hz, 1H, Pyr), 8.23
(OCH CH ) ), 1.82 and 1.92 (m, 2H, NCH CH CH Si),
2 3 3 2 2 2
H
H‐H