124
A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ126
/
5.6 Hz, arom. CHp-cymene); 1.87 (s, 3H, Mep-cymene); 1.10
(d, 3JHH 6.7 Hz, 3H, CHMe2,p-cymene); 0.94 (d, 3JHH
7.1 Hz, 3H, CHMe2,p-cymene).
C37H39ClF3N2O3PRuS (815.89): C, 54.46; H, 4.82; N,
3.43. Found: C, 54.64; H, 4.92; N, 3.23%. 31P{1H}-
ꢁ
/
ꢁ
/
1
NMR (CDCl3): d 61.2 (s). H-NMR (CDCl3): 8.63 (d,
3
3
1H, JHH
H6?); 7.98ꢂ
CꢂCH2); 1.85ꢂ
4JHP 0.9 Hz, 18H, C6Me6). 13C{1H}-NMR (CDCl3):
ꢁ
ꢁ
/
5.4 Hz, H6?); 8.42 (d, 1H, JHH
ꢁ
/
4.6 Hz,
2.81 (m, 4H,
CH2); 1.82 (d,
4.2.2. [RuCl(p-cymene)(NPN)]BF4 (2)
/
7.54 (m, Ph and pyridine); 3.32ꢂ
/
Phosphole NPN (0.150 g, 0.41 mmol) and AgBF4
(0.079 g, 0.41 mmol) were added to a solution of [Ru(p-
cymene)Cl2]2 (0.125 g, 0.20 mmol) in dichloromethane
(20 ml). The reaction mixture was stirred at r.t. for 1 h.
The precipitate of AgCl was filtered off and the obtained
solution was evaporated to dryness. A brown solid of 2
Ä
/
/
/
2.20 (m, 4H, ÄCꢂCH2ꢂ
/
/
/
/
155.00 (s, C6?); 150.00 (s, C6?); 140.85 (s, C4?); 139.37 (s,
C4?); 133.52 (d, JCP
ꢁ9.0 Hz, Cortho-Ph); 131.98 (d,
2.6 Hz, Cpara-Ph); 127.35 (d, JCP
/
2
4JCP
meta-Ph); 125.71 (s, C5?); 124.10 (s, C5?); 123.80 (d,
3JCP 7.4 Hz, C3?); 123.44 (d, 3JCP 7.4 Hz, C3?); 98.74
(s, C6Me6); 29.95 (d, 3JCP
6.5 Hz, ÄCꢂCH2); 27.41 (d,
3JCP
8.3 Hz, ÄCꢂCH2); 22.21 (s, ÄCꢂCH2ꢂCH2);
21.90 (s, ÄCꢂCH2ꢂCH2); 15.42 (s, C6Me6).
ꢁ
/
ꢁ
/
10.6 Hz,
3
C
was obtained after washing with pentane (2ꢅ
Yield, 238.0 mg (82%). Anal. Calc.
/
10 ml).
for
ꢁ
/
ꢁ
/
ꢁ
/
/
/
C34H35BClF4N2PRu (725.67): C, 56.27; H, 4.82; N,
3.86. Found: C, 56.55; H, 4.76; N, 3.96%. IR (cmꢄ1):
1570 (nCNphosphole); 1055 (BF4). 2a: 31P{1H}-NMR
ꢁ
/
/
/
/
/
/
/
/
/
1
(CDCl3): d 65.6 (s). H-NMR (CDCl3): 9.16 (d, 1H,
5.2 Hz, H6?); 8.70 (d, 1H, JHH
4.2.4. Ru(C5H5)Cl(NPN) (4)
3
3JHH
ꢁ
/
ꢁ
/
4.2 Hz, H6?);
Phosphole NPN (0.149 g, 0.40 mmol) was added to a
solution of Ru(C5H5)Cl(cod) (0.125 g, 0.40 mmol) in
THF (20 ml). The reaction mixture was stirred at 40 8C
for 2 h. After evaporation to dryness and washing with
pentane (10 ml), 4 was obtained as a brown solid. Yield,
182.3 mg (80%). Anal. Calc. for C29H26ClN2PRu
(569.81): C, 61.12; H, 4.56; N, 4.91. Found: C, 61.07;
H, 4.64; N, 4.86%. IR (cmꢄ1): 1560, 1525
(nCNphosphole). 31P{1H}-NMR ((CD3)2CO): d 82.2 (s,
7.95 ꢂ
/
7.53 (m, Ph and pyridine); 5.97 (d, 1H, 3JHH
ꢁ
/
6.1
5.6 Hz,
5.6 Hz, arom.
CHp-cymene); 5.47 (m, 1H, arom. CHp-cymene); 2.47 (sept.,
1H, CHMe2,p-cymene); 3.22ꢂ2.73 (m, 4H, ÄCꢂCH2);
1.95ꢂ1.84 (m, 4H, ÄCꢂCH2ꢂCH2); 1.61 (3H, Mep-
cymene); 1.22 (d, JHH 7.1 Hz, 3H, CHMe2,p-cymene);
3
Hz, arom. CHp-cymene); 5.92 (d, 1H, JHH
ꢁ
/
3
arom. CHp-cymene); 5.78 (d, 1H, JHH
ꢁ
/
/
/
/
/
/
/
/
3
ꢁ
/
3
1.27 (d, JHH
NMR (CDCl3): 159.54 (s, C6?); 150.00 (s, C6?); 140.00 (s,
ꢁ
6.8 Hz, 3H, CHMe2,p-cymene). 13C{1H}-
/
1
4b); 68.6 (s, 4a); H-NMR ((CD3)2CO): 9.53 (d, 1H,
C4?); 137.00 (s, C4?); 133.10 (d, JCP
ꢁ
/
8.1 Hz, Cortho-Ph);
3JHH
ꢁ
/
5.6 Hz, H6?, 4b); 9.34 (d, 1H, 3JHH
ꢁ
5.6 Hz, H6?,
/
2
4
131.98 (d, JCP
3
2 Hz, Cpara-Ph); 128.12 (d, JCP
ꢁ
/
ꢁ/10.0
4b); 8.65 (m, 2H, H6?, 4a); 7.9ꢂ
4a and 4b); 4.6 (s, C5H5, 4a); 4.1 (C5H5, 4b); 3.32ꢂ
(m, 4H, ÄCꢂCH2, 4a and 4b); 2.05ꢂ1.61 (m, 4H, Ä
/
6,8 (m, Ph and pyridine,
2.80
Cꢂ
Hz, Cmeta-Ph); 125.15 (s, C5?); 124.10 (s, C5?); 123.80 (d,
/
3
3JCP
110.85 (s, Cipso
cymene); 94.75 (m, CHp-cymene); 94.15 (d, JCP
ꢁ
/
7.5 Hz, C3?); 123.44 (d, JCP
ꢁ
/
7.5 Hz, C3?);
/
/
/
/
/
ꢂ
/
CH3,p-cymene); 97.15 (s, Cipso ꢂi
/
Prp-
7.5 Hz,
CH2ꢂ
CH2, 4a and 4b). 13C{1H}-NMR ((CD3)2CO):
/
2
ꢁ
/
159.29 (s, C6?, 4b); 159.27 (s, C6?, 4a); 150.31 (s, C6?, 4b);
CHp-cymene); 87.81 (s, CHp-cymene); 83.68 (s, CHp-
150.30 (s, C6?, 4a); 137.20 (s, 2C), 135.36 (s) and 134.34
3
cymene); 31.5 (s, CHMe2,p-cymene); 29.95 (d, JCP
2
ꢁ
/
10.0
CH2);
CH2);
(s) (C4?, 4a and 4b); 134.25 (d, JCP
ꢁ11.0 Hz, Cortho-Ph,
/
3
CH2); 27.84 (d, JCP
2
4b); 132.84 (d, JCP
Hz, Ä
/
Cꢂ
/
ꢁ
/
7.5 Hz, Ä
/
Cꢂ
/
ꢁ11.0 Hz, Cortho-Ph, 4a); 130.26 (d,
/
3
1.9 Hz, Cpara-Ph, 4a and 4b); 129.02 (d, JCP
24.12 (s, CHMe2,p-cymene); 23.00 (s, Ä
/
CꢂCH2ꢂ
/
/
4JCP
10.0 Hz, Cmeta-Ph, 4a); 128.18 (d, JCP
ꢁ
/
ꢁ
/
3
22.00 (s, Ä
/
Cꢂ
/
CH2ꢂ
/
CH2); 21.22 (s, CHMe2,p-cymene);
18.36 (s, Mep-cymene). 2b: 31P{1H}-NMR (CDCl3): d
ꢁ10.1 Hz, Cmeta-
/
3
Ph, 4b); 125.04 (d, JCP
3JCP
4b); 122.32 (d, 3JCP
(s), 121.85 (s) and 120.81 (s) (C5?, 4a and 4b); 75.44 (s,
C5H5, 4a); 73.45 (s, C5H5, 4b); signal of ÄCꢂCH2 of 4a
must be overlapped with the solvent signal; 27.40 (2C, Ä
CꢂCH2, 4b) 23.85 (2C, ÄCꢂCH2ꢂCH2, 4a); 23.12 (2C,
CꢂCH2ꢂCH2, 4b).
ꢁ
/
7.0 Hz, C3?, 4a); 124.91 (d,
1
69.6 (s). H-NMR (CDCl3, only assigned resonances):
3
ꢁ
/
8.0 Hz, C3?, 4a); 124.87 (d, JCP
ꢁ
7.0 Hz, C3?,
/
9.59 (d, 1H, 3JHH
ꢁ
/
5.1 Hz, H6?); 8.70 (d, 1H, 3JHH
ꢁ
/4.3
ꢁ
7.0 Hz, C3?, 4b); 122.17 (s), 122.12
/
Hz, H6?); 6.27 (d, 1H, JHH
ꢁ6.8 Hz, CHp-cymene); 6.05
/
3
(d, 1H, 3JHH
6.3 Hz, CHp-cymene); 1.86 (3H, Mep-cymene); 1.07 (d,
3JHH 6.8 Hz, 3H, CHMe2,p-cymene); 0.96 (d, 3JHH
7.1
ꢁ
/
6.3 Hz, CHp-cymene); 5.85 (d, 1H, 3JHH
ꢁ
/
/
/
/
ꢁ
/
ꢁ
/
/
/
/
/
Hz, 3H, CHMe2,p-cymene).
Ä
/
/
/
4.2.3. [RuCl(C6Me6)(NPN)]TfO (3)
4.2.5. Ru(C5Me5)Cl(NPN) (5)
Phosphole NPN (0.165 g, 0.45 mmol) and AgTfO
(0.116 g, 0.45 mmol) were added to a solution of
[Ru(C6Me6)Cl2]2 (0.150 g, 0.22 mmol) in dichlorome-
tane (20 ml). The reaction mixture was stirred at r.t. for
2 h. The precipitate of AgCl was filtered off and the
obtained solution was evaporated to dryness. A orange
Phosphole NPN (0.208 g, 0.57 mmol) was added to a
solution of Ru(C5Me5)Cl(cod) (0.215 g, 0.57 mmol) in
THF (20 ml). The reaction mixture was stirred at 40 8C
for 3 h. After evaporation to dryness and washing with
pentane (10 ml), 5 was obtained as a brown solid. Yield,
310.0 mg (85%). Anal. Calc. for C34H36ClN2PRu
(639.86): C, 63.82; H, 5.62; N, 4.37. Found: C, 64.01;
H, 5.64; N, 4.42%. IR (cmꢄ1): 1555, 1510
solid of 3 was obtained after washing with pentane (2ꢅ
/
10 ml). Yield, 305.1 mg (85%). Anal. Calc. for