I. Warad et al. / Inorganica Chimica Acta 357 (2004) 1847–1853
1849
tube. The solid mixture was stirred and warmed for 5
min, then 20 ml of dichloromethane was added and the
solution was stirred for 5 min. After filtration through
silica the solution was concentrated to about 2 ml under
reduced pressure. The corresponding cationic complex
was precipitated by addition of 30 ml of diethyl ether,
filtered off (P3), washed three times with 25 ml portions
of diethyl ether, and dried under vacuum.
(b) A solution of AgBF4 (5% excess) in 25 ml of di-
chloromethane was added to a solution of the neutral
complexes 1L1, 1L3, 1L6, and 1L7 [9] in 25 ml of di-
chloromethane and the solution was stirred for 4 h.
After filtration through silica the solution was concen-
trated to a small volume (2 ml). The addition of 100 ml
of diethyl ether caused the precipitation of a solid, which
was filtered off (P3), washed three times with 25 ml
portions of diethyl ether, and dried under vacuum.
(m, 14H, CH2P, OCH2, H2NCH), 2.86, 2.94, 4.1, 4.3
(4s, 6H, OCH3), 6.3–7.7 (m, 30H, C6H5). 31P{1H} NMR
(CD2Cl2): isomer a (80%), d (ppm) 58.4 (d, 2JPP ¼ 37:23
2
Hz), 47.5 (d, JPP ¼ 37:23 Hz); isomer b (20%), 54.4 (d,
2
2JPP ¼ 37:23 Hz), 47.4 (d, JPP ¼ 37:23 Hz). 13C{1H}
NMR (CD2Cl2): 23.1–32.4 (m, PCH2), 58.3–69.3 (8s,
H2NCH, OCH3), 68.61, 69.25, 74.21, 74.63 (4d,
3JPC ¼ 4:52 Hz, CH2O), 126.6–130.1 (C6H5). FAB-MS:
(m=z) 837.2 (Mþ ) OTf). Anal. Calc. for C45H50ClF3-
N2O5SP2Ru: C, 54.79; H, 5.11; Cl, 3.59; N, 2.84; S, 3.25.
Found: C, 54.74; H, 5.37; Cl, 3.47; N, 2.97; S, 3.59%.
2.2.5. 2L5
Complex 1L5 (300 mg, 0.344 mmol) was treated with
AgOTf (89 mg, 0.346 mmol) to give 2L5. Yield 320 mg
1
(96%) of a yellow powder. H NMR (CD2Cl2): 0.7–4.6
(m, 14H, CH2P, OCH2, H2NCH), 2.88, 2.97, 4.2, 4.4
(4s, 6H, OCH3), 6.5–7.8 (m, 30H, C6H5). 31P{1H} NMR
(CD2Cl2): isomer a (80%), d (ppm) 58.5 (d, 2JPP ¼ 37:23
2.2.1. 2L1
Complex 1L1 (300 mg, 0.401 mmol) was treated with
AgBF4 (79 mg, 0.406 mmol) to give 2L1. Yield 244 mg
2
Hz), 47.7 (d, JPP ¼ 37:23 Hz); isomer b (20%), 54.8 (d,
2
2JPP ¼ 37:23 Hz), 47.6 (d, JPP ¼ 37:23 Hz). 13C{1H}
1
(77%) of a yellow powder. H NMR (CD2Cl2): 2.0–4.0
NMR (CD2Cl2): 24.2–32.8 (m, PCH2), 58.7–69.2 (8s,
H2NCH, OCH3), 68.62, 69.26, 74.30, 74.58 (4d,
3JPC ¼ 4:52 Hz, CH2O), 127.6–131.4 (C6H5). FAB-MS:
(m=z) 837.2 (Mþ ) OTf). Anal. Calc. for C45H50ClF3-
N2O5SP2Ru: C, 54.79; H, 5.11; Cl, 3.59; N, 2.84; S, 3.25.
Found: C, 54.70; H, 5.30; Cl, 3.67; N, 2.98; S, 3.60%.
(m, 14H, CH2P, H2NCH2CNH2, CH2O), 0.99, 1.10,
1.18, 1.24 (4s, 6H, C(CH3)2), 2.98, 3.06, 3.71, 3.79 (4s,
6H, OCH3), 6.42–8.21 (m, 20H, C6H5). 31P{1H} NMR
(CD2Cl2): isomer a (67%), d (ppm) 56.6 (d, 2JPP ¼ 38:14
2
Hz), 48.7 (d, JPP ¼ 38:14 Hz); isomer b (33%), 55.6 (d,
2
2JPP ¼ 37:23 Hz), 47.0 (d, JPP ¼ 37:23 Hz). FAB-MS:
(m=z) 713.2 (Mþ ) BF4). Anal. Calc. for C34H46BClF4-
N2O2P2Ru: C, 51.05; H, 5.79; Cl, 4.43; N, 3.50. Found:
C, 51.11; H, 5.71; Cl, 4.34; N, 3.50%.
2.2.6. 2L6
Complex 1L6 (300 mg, 0.394 mmol) was treated with
AgBF4 (78 mg, 0.401 mmol) to give 2L6. Yield 224 mg
1
(70%) of a yellow powder. H NMR (CD2Cl2): d (ppm)
2.2.2. 2L2
Complex 1L2 (300 mg, 0.387 mmol) was treated with
AgOTf (100 mg, 0.389 mmol) to give 2L2. Yield 313 mg
0.42, 0.83 (2s, 6H, CH3), 1.2–3.7 (m, 16H, CH2P,
H2NCH2, CH2O), 3.00, 3.66 (2s, 6H, OCH3), 6.4–8.1
(m, 20H, C6H5). 31P{1H} NMR (CD2Cl2): d (ppm) 51.4
(d, 2JPP ¼ 37:21 Hz), 43.0 (d, 2JPP ¼ 37:21 Hz). 13C{1H}
NMR (CD2Cl2): 18.41, 25.37 (2s, 2CH3), 23.88, 29.54
1
(91%) of a yellow powder. H NMR (CD2Cl2): 0.8–4.0
(m, 22H, CH2P, H2NCHCH2CH2, CH2O), 2.89, 3.10,
3.64, 3.70 (4s, 6H, OCH3), 6.4–8.1 (m, 20H, C6H5).
31P{1H} NMR (CD2Cl2): isomer a (80%), d (ppm) 58.7
(d, 2JPP ¼ 37:23 Hz), 48.3 (d, 2JPP ¼ 37:23 Hz); isomer b
1
(2d, JPC ¼ 4:4 Hz, PCH2), 47.16, 50.75 (2s, NCH2),
3
56.81, 58.75 (2s, OCH3), 66.54, 71.55 (2d, JPC ¼ 4:50
Hz, CH2O), 126.4-135.4 (C6H5). FAB-MS: (m=z) 727.2
(Mþ ) BF4). Anal. Calc. for C35H48BClF4N2O2P2Ru: C,
51.64; H, 5.94; Cl, 4.36; N, 3.44. Found: C, 51.20; H,
5.60; Cl, 4.28; N, 3.05%.
2
2
(20%), 56.8 (d, JPP ¼ 37:23 Hz), 49.4 (d, JPP ¼ 37:23
Hz). 13C{1H} NMR (CD2Cl2): 24.2–36.3 (8s, NH2-
CHCH2CH2), 30.1–36.0 (m, PCH2), 56.9–61.7 (8s,
NCH, OCH3), 68.29, 68.85, 73.79, 74.25 (4d, JPC
4:88 Hz, CH2O), 128.2–131.4 (C6H5). FAB-MS: (m=z)
739.2 (Mþ ) OTf). Anal. Calc. for C37H48ClF3N2O5-
SP2Ru: C, 50.03; H, 5.45; Cl, 3.99; N, 3.15; S, 3.61.
Found: C, 50.17; H, 5.35; Cl, 4.20; N, 3.07; S, 3.48%.
3
¼
2.3. General procedure for the catalytic studies
The amount (0.026 mmol) of the respective di-
amine(ether–phosphine)ruthenium(II) complex 1L1–1L7
[5] was placed in a 50-ml Schlenk tube and solid AgOTf
or AgBF4 (0.026 mmol) was added. The Schlenk tube
was evacuated several times and filled with argon. After
that 5 ml of CH2Cl2 was added and the mixture was
stirred (2 min in case of AgOTf and 2 h in case of
AgBF4). Subsequently, AgCl was filtered off (P3) and the
solution was transferred to a 200-ml Schlenk tube. Then
CH2Cl2 was completely removed in vacuum. Afterwards
2.2.3. 2L3 and 2L7
See [7].
2.2.4. 2L4
Complex 1L4 (300 mg, 0.344 mmol) was treated with
AgOTf (89 mg, 0.346 mmol) to give 2L4. Yield 319 mg
1
(95%) of a yellow powder. H NMR (CD2Cl2): 0.7–4.3