60
E. Becker et al. / Journal of Organometallic Chemistry 649 (2002) 55–63
3.2. Syntheses
(12.7 ml, 0.147 mmol) as the starting materials. Yield:
90 mg (86%). Anal. Calc. for C26H25BrF6PRuSb: C,
1
3.2.1. [RuCp(AsPh3)(CH3CN)2]PF6 (2b)
39.77; H, 3.21. Found: C, 39.79; H, 3.24%. H-NMR
A solution of 1 (240 mg, 0.552 mmol) and AsPh3
(169 mg, 0.552 mmol) in CH2Cl2 (5 ml) has been stirred
at room temperature (r.t.) for 2 h. After that time the
volume of the solution was reduced to about 0.5 ml.
Upon addition of Et2O (5 ml) a yellow precipitate was
formed, which was collected on a glass frit, washed
twice with Et2O, and dried under vacuum. Yield: 365
mg (95%). Anal. Calc. for C27H26AsF6N2PRu: C, 46.36;
H, 3.75; N, 4.01. Found: C, 46.38; H, 3.80; N, 3.98%.
1H-NMR (l, acetone-d6, 20 °C): 7.74–7.20 (m, 15H,
Ph), 4.43 (s, 5H, Cp), 2.41 (s, 6H, CH3). 13C{1H}-NMR
(l, acetone-d6, 20 °C): 135.3 (6C, Ph2,6), 133.9 (d, 3C,
Ph1), 130.9 (3C, Ph4), 129.7 (6C, Ph3,5), 129.3 (2C,
NꢂC), 74.1 (5C, Cp), 3.3 (2C, CH3). IR (KBr, cm−1):
wCN 2284 (m).
(l, acetone-d6, 20 °C): 7.66–7.50 (m, 15H, Ph), 6.26 (s,
3
5H, Cp), 4.74 (d, Jtrans=10.7 Hz, 1H, CH2CHCH2),
4.36 (dd, 3Jcis=6.3 Hz, 4Jallyl=2.7 Hz, 1H,
CH2CHCH2), 4.33–4.20 (m, 1H, CH2CHCH2), 4.16
3
4
(dd, Jcis=6.3 Hz, Jallyl=2.7 Hz, 1H, CH2CHCH2),
3.50 (d, Jtrans=10.7 Hz, 1H, CH2CHCH2). 13C{1H}-
3
NMR (l, acetone-d6, 20 °C): 136.5 (6C, Ph2,6), 136.1
(3C, Ph1), 132.6 (3C, Ph4), 130.8 (6C, Ph3,5), 96.1 (1C,
CH2CHCH2), 92.5 (5C, Cp) 63.6 (1C, CH2CHCH2),
48.9 (1C, CH2CHCH2).
3.2.5. [RuCp(p6-PhBiPh2)]PF6 (4a)
Compound 4a could not be isolated and was charac-
terized by NMR spectroscopies from a mixture of 4a
and 4b from the reaction of 1 with one equivalent of
1
3.2.2. [RuCp(SbPh3)(CH3CN)2]PF6 (2c)
BiPh3 at r.t. H-NMR (l, CD3NO2, 20 °C): 7.92 (d,
3
This complex has been prepared analogously to 2b
with 1 (240 mg, 0.552 mmol) and SbPh3 (195 mg, 0.552
mmol) as the starting materials. Yield: 380 mg (92%).
Anal. Calc. for C27H26F6N2PRuSb: C, 43.45; H, 3.51;
3JHH=8.0 Hz, 4H, Ph2,6), 7.56 (t, JHH=8.0 Hz, 4H,
3
Ph3,5), 7.44 (d, JHH=8.0 Hz, 2H, Ph4), 6.46–6.16 (m,
5H, h6-Ph), 5.26 (s, 5H, Cp). 13C{1H}-NMR (l,
CD3NO2, 20 °C): 138.5 (4C, Ph2,6), 132.1 (4C, Ph3,5),
129.6 (2C, Ph4), not observed (2C, Ph1), 94.1 (2C,
h6-Ph2,6), 88.9 (2C, h6-Ph3,5), 85.8 (1C, h6-Ph4), not
observed (1C, h6-Ph1), 81.2 (5C, Cp).
1
N, 3.75. Found: C, 43.41; H, 3.57; N, 3.81%. H-NMR
(l, CDCl3, 20 °C): 7.51–7.41 (m, 15H, Ph), 4.59 (s, 5H,
Cp), 2.20 (s, 6H, CH3). 13C{1H}-NMR (l, acetone-d6,
20 °C): 136.3 (6C, Ph2,6), 132.2 (3C, Ph1), 131.1 (3C,
Ph4), 130.3 (6C, Ph3,5), 130.2 (2C, NCꢀCH3), 72.6 (5C,
Cp), 3.6 (2C, CH3). IR (KBr, cm−1): wCN 2283 (m).
3.2.6. [(RuCp)2(v-p6,p6-Ph2BiPh)](PF6)2 (4b)
A solution of 1 (100 mg, 0.230 mmol) and BiPh3 (51
mg, 0.115 mmol) in nitromethane (4 ml) was stirred for
4 h at 80 °C. After that time the volume of the solution
was reduced to about 0.1 ml. Upon addition of Et2O (5
ml) a yellow precipitate was formed, which was col-
lected on a glass frit, washed with Et2O, and dried
under vacuum. Yield: 106 mg (86%). Anal. Calc. for
C28H25BiF12P2Ru2: C, 31.65; H, 2.37. Found: C, 31.42;
H, 2.35%. 1H-NMR (l, CD3NO2, 20 °C): 8.07 (d,
3JHH=7.3 Hz, 2H, Ph2,6), 7.71 (t, 3J=7.3 Hz, 2H,
Ph3,5), 7.53 (d, 3J=7.3 Hz, 1H, Ph4), 6.46–6.16 (m,
10H, h6-Ph), 5.33 (s, 10H, Cp). 13C{1H}-NMR (l,
CD3NO2, 20 °C): 138.4 (2C, Ph2,6), 132.7 (2C, Ph3,5),
130.5 (1C, Ph4), not observed (1C, Ph1), 94.2, 93.9 (4C,
h6-Ph2,6), 89.6, 89.3 (4C, h6-Ph3,5), 86.3 (2C, h6-Ph4),
not observed (2C, h6-Ph1), 81.7 (10C, Cp).
3.2.3. [RuCp(p3-CH2CHCH2)(AsPh3)Br]PF6 (3b)
To a solution of 2b (100 mg, 0.143 mmol) in 5 ml of
CH2Cl2 was slowly added BrCH2CHꢁCH2 (13.6 ml,
0.157 mmol). The mixture was stirred at r.t. for 5 h.
The solvent was then removed in vacuo and the residue
redissolved in CH2Cl2 (0.5 ml). On slow addition of
n-hexane (5 ml) an orange precipitate was formed,
which was collected on a glass frit, washed with n-hex-
ane (4×1 ml), and dried in vacuo. Yield: 102 mg
(97%). Anal. Calc. for C26H25AsBrF6PRu: C, 42.30; H,
1
3.41. Found: C, 42.38; H, 3.38%. H-NMR (l, acetone-
d6, 20 °C): 7.70–7.36 (m, 15H, Ph), 6.21 (s, 5H, Cp),
3
4.82 (d, Jtrans=11.0 Hz, 1H, CH2CHCH2), 4.54 (dd,
4
3Jcis=6.3 Hz, Jallyl=2.8 Hz, 1H, CH2CHCH2), 4.23–
3
4.04 (m, 1H, CH2CHCH2), 3.96 (dd, Jcis=6.3 Hz,
3
4Jallyl=2.6 Hz, 1H, CH2CHCH2), 3.78 (d, Jtrans=11.1
Hz, 1H, CH2CHCH2). 13C{1H}-NMR (l, acetone-d6,
20 °C): 134.2 (6C, Ph2,6), 133.8 (3C, Ph1) 132.5
(3C,Ph4), 130.4 (6C, Ph3,5), 97.3 (1C, CH2CHCH2),
94.3 (5C, Cp) 67.1 (1C, CH2CHCH2), 53.7 (1C,
CH2CHCH2).
3.2.7. [RuCp(PPh3)2(CH3CN)]PF6 (5a)
A solution of 2a (100 mg, 0.153 mmol) in benzene (4
ml) was stirred for 72 h at 80 °C. The solvent was
removed in vacuum and the residue was purified by
column chromatography (eluent CH2Cl2–Me2CO 10:1
(v/v) sampling the yellow band). Removal of the sol-
vent and drying in vacuum gave a yellow powder.
Yield: 47 mg (35%) [7].
3.2.4. [RuCp(p3-CH2CHCH2)(SbPh3)Br]PF6 (3c)
This complex has been prepared analogously to 3b
with 2c (100 mg, 0.134 mmol) and BrCH2CHꢁCH2