120
A.R. Kudinov et al. / Journal of Organometallic Chemistry 657 (2002) 115ꢂ122
/
4
(
.3. Synthesis of (h-9-SMe -7,8-C B H )Rh(CO)I
10
4.6. Synthesis of (h-9-SMe -7,8-C B H )Rh(h-7,8-
2 2 9 10
2
2
9
2
5)
C B H11) (9)
2 9
Carbon monoxide was bubbled through a suspension
of [(h-9-SMe -7,8-C B H )RhI ] (55 mg, 0.05 mmol)
MeCN (5 ml) was added to a mixture of [(h-9-SMe
7,8-C 10)RhCl
(74 mg, 0,1 mmol) and Tl[Tl(h-
,8-C B H )] (135 mg, 0.25 mmol), and the reaction
2
-
B
H
]
2 2
2
2
9
10
2 2
2
9
7
in THF (5 ml) for 2 h leading to dissolution of the
starting material and color change from purple to
brown. After filtration, petroleum ether was added to
precipitate the product, which was washed with petro-
leum ether and dried in vacuo. Yield 51 mg (89%). The
2
9
11
mixture was stirred for 48 h. After filtration, solvent was
removed in vacuo and the residue was dissolved in
acetone and filtered through a short layer (5 cm) of
Al O . The resulting solution was reduced in volume to
2
3
1
11
ca. 2 ml and ether was added to precipitate white solid,
which was filtered off, washed with ether and dried in
vacuo. Yield 67 mg (78%). MS (several sets of peaks
corresponding to the isotopic distribution were ob-
H- and B-NMR spectroscopy confirmed the identity
and purity of 5 [10].
served; only the highest peaks are given): m/zꢁ
/
429
SMe2Ã
C B H ] ). Anal. Calc. for C H B RhS: C, 16.80;
ꢃ
ꢃ
4
(
.4. Synthesis of (h-9-SMe -7,8-C B H )Rh(PPh )Cl
2
[M ], 297 ([Mꢀ
/
C B H ] ), 234 ([Mꢀ
/
/
2
9
10
3
2
2
9
11
ꢃ
6a)
2
9
10
6
27 18
H, 6.35; B, 45.38. Found: C, 16.67; H, 6.63; B, 45.60%.
1
1
1
A suspension of [(h-9-SMe -7,8-C B H )RhCl ] (37
B{ H}-NMR d/ppm ((CD ) CO): dꢁ
/
ꢀ
/
22.03 (bs,
18.16 (bs, 1B), ꢀ17.26 (bs,
14.74 (bs, 1B), ꢀ9.29 (bs, 1B),
4.60 (bs, 3B), ꢀ2.96 (bs, 1B), ꢀ1.47
2
2
9
10
2 2
3 2
mg, 0.05 mmol) and PPh (27 mg, 0.1 mmol) in CH Cl
2
1B), ꢀ
1B), ꢀ15.44 (bs, 1B), ꢀ
5.51 (bs, 2B), ꢀ
/
21.04 (bs, 1B), ꢀ
/
/
3
2
(
10 ml) was stirred overnight. The red solution was
/
/
/
filtered and petroleum ether was added to precipitate the
crude product as a microcrystalline solid, which was
filtered off, washed with ether and dried in vacuo. An
analytically pure sample was obtained by reprecipitation
of the crude product by petroleum ether from CH Cl .
ꢀ
/
/
/
/
(bs, 1B), 0.74 (bs, 1B), 4.33 (bs, 1B), 5.51 (bs, 1B), 8.49
(bs, 1B).
4.7. Synthesis of [CpRh(h-9-SMe -7,8-
C B H )]CF SO (11aCF SO )
2
2
2
Yield 57 mg (90%). Anal. Calc. for C H B Cl PRhS:
2
2
9
10
3
3
3
3
2
2
31
9
C, 41.97; H, 4.96; B, 15.45. Found: C, 42.10; H, 5.18; B,
1
1
1
Acetone (10 ml) was added to a mixture of [(h-9-
1
5.30%.
B{ H}-NMR d/ppm ((CD ) CO): dꢁ
/
3
2
SMe -7,8-C B H )RhCl ] (73 mg, 0.1 mmol) and
CF SO Ag (103 mg, 0.4 mmol). An immediate precipi-
2
2
9
10
2 2
ꢀ
/
20.39 (bs, 2B), ꢀ
/
14.79 (bs, 1B), ꢀ
0.79 (bs, 2B), 4.18 (bs, 1B), 6.26 (bs,
35.41, 34.66 (d,
/
8.85 (bs, 1B),
3
3
ꢀ
/
4.82 (bs, 1B), ꢀ
/
31
tation of AgCl occurs. The suspension was stirred for 1
h and cyclopentadiene (0.3 ml, excess) was added. The
reaction mixture was stirred overnight. After filtration
solvent was removed in vacuo and the residue was
reprecipitated twice by ether from CH Cl to give 53 mg
1
B). P-NMR d/ppm ((CD ) CO): dꢁ
/
3
2
1
P, Jꢁ
/
121.1 Hz, Rh).
2
2
4
.5. Synthesis of [(h-9-SMe -7,8-
2
(52%) of very pale yellow microcrystalline solid. Anal.
Calc. for C10 RhS : C, 23.52; H, 4.15; B,
9.06. Found: C, 23.78; H, 4.22; B, 19.01%. B{ H}-
NMR d/ppm ((CD CO): dꢁ 22.26 (bs, 1B), ꢀ18.27
(bs, 1B), ꢀ16.82 (bs, 1B), ꢀ9.79 (bs, 1B), ꢀ5.76 (bs,
1B), ꢀ3.48 (bs, 1B), 1.23 (bs, 1B), 2.87 (bs, 1B), 4.85 (bs,
C B H )Rh(dppe)Cl]BF (7BF )
2
H
21
B
9
F
3
O
3
2
9
10
4
4
1
1
1
1
MeCN (5 ml) was added to a mixture of [(h-9-SMe2-
3
)
2
/
ꢀ
/
/
7
,8-C B H )RhCl ] (37 mg, 0,05 mmol), TlBF (29 mg,
.1 mmol) and PPh CH CH PPh (40 mg, 0.1 mmol).
/
/
/
2
9
10
2 2
4
0
/
2
2
2
2
1
B).
An immediate precipitation of TlCl occurs. The reaction
mixture was stirred overnight. After filtration solvent
was removed in vacuo and the residue was recrystallized
4.8. Synthesis of [Cp*Rh(h-9-SMe -7,8-C B H )]X
2
(
2
9
10
11bX)
from hot methanolꢂ
55%) of orange crystals. Anal. Calc. for
C H B ClF P RhS: C, 44.10; H, 4.93; B, 13.23.
/
benzene mixture to give 45 mg
(
4
.8.1. Method 1, Xꢁ
[Cp*RhCl (56 mg, 0.09 mmol) was dissolved in
THF (5 ml) and a solution of Na[9-SMe -7,8-C B H ]
/PF6
3
0
40 10
4 2
1
1
1
]
2 2
Found: C, 43.88; H, 5.29; B, 13.10%. B{ H}-NMR
d/ppm ((CD ) CO): dꢁ 24.68 (bs, 1B), ꢀ12.40 (bs,
5.58 (bs, 2B), ꢀ0.15 (bs, 1B,
BF ), 3.86 (bs, 1B), 8.24 (bs, 1B). P-NMR d/ppm
2
2
9
10
/
ꢀ
/
/
3
2
in THF (1.2 ml of 0.17 M solution, 0.2 mmol) was
added. The reaction mixture was stirred overnight. After
the solvent was removed in vacuo, the residue was
1
B), ꢀ
/
7.70 (bs, 3B), ꢀ
/
/
ꢀ
31
4
(
(CD ) CO): dꢁ
/
65.24, 65.82 (d, 1P, Jꢁ
6.65, 76.78, 77.54, 77.67 (d of d, 1P, Jꢁ
21.87 Hz, P).
/
95.1 Hz, Rh).
144.6 Hz, Rh;
3
2
dissolved in H O (3 ml) and filtered. Excess of a solution
2
7
/
of NH PF in water was added to precipitate white
4
6
Jꢁ
/
solid, which was filtered off, washed with water, and
Kudinov, Alexander R
