138
A.S. Romanov et al. / Journal of Organometallic Chemistry 715 (2012) 136e140
PPh3 possess moderate structural trans-effect vs. halide anions in
accordance with general tendency [19].
2-Me). 11B{1H} NMR (CD2Cl2):
cmꢀ1): 1027 (SO). IR ( , acetone solution, KBr, cmꢀ1): 902 (SO).
d
¼ 16.05 (bs). IR (
n, solid sample, KBr,
n
4.2.2. CpCo(m-1,3-C3B2Me5)MX2PPh3
3. Conclusion
(9) M ¼ Rh; X ¼ Cl. The CH2Cl2 (2 ml) was added to a mixture of
complex 1 (0.043 g, 0.05 mmol) and PPh3 (0.026 g, 0.1 mmol). The
reaction mixture was stirred for 12 h and then filtered. The product
was precipitated by addition of Et2O (20 ml), centrifuged, washed
with Et2O and dried in vacuo. Yield 0.057 g (83%). Dark-green solid.
C31H35B2Cl2CoRhP (692.96): calcd. C 53.73, H 5.09, B 3.12; found C
The reactions of the halide complexes 1e4 with 2-electron
donor ligands Me2SO and PPh3 allowed to prepare the triple-
decker type adducts CpCo(
m
-1,3-C3B2Me5)MX2L (L ¼ Me2SO and
PPh3). The IR spectroscopy revealed the tautomeric behavior for
dimethylsulfoxide ligand (S or O coordination) in adducts 5e8. The
X-ray diffraction study of adducts 5e12 showed that the Me2SO and
PPh3 ligands possess moderate structural trans-effect, whereas
53.90, H 5.22, B 3.04. 1H NMR (CD2Cl2):
d
¼ 7.62e7.68 (m, 6H, PPh3),
7.37e7.47 (m, 6H, PPh3), 7.05e7.20 (m, 3H, PPh3), 4.68 (s, 5H, CpCo),
2.35 (s, 6H, 4,5-Me), 1.09 (s, 6H,1,3-BMe), 0.58 (s, 3H, 2-Me). 11B{1H}
halogen atoms show weak trans-effect in the presence of [CpCo(m-
1,3-C3B2Me5)] sandwich unit.
NMR (CD2Cl2):
d
¼ 21.27 (s). 31P{1H} NMR (CD2Cl2):
d
¼ 29.84 (d,
1JRhP ¼ 161,0 Hz).
(10) M ¼ Ir; X ¼ Cl. Complex 10 was prepared similarly to 9 from
complex 2 (0.062 g, 0.06 mmol) and PPh3 (0.032 g, 0.12 mmol).
Yield 0.085 g (91%). Dark-brown solid. C31H35B2Cl2CoIrP (782.27):
calcd. C 47.60, H 4.51, B 2.76; found C 47.51, H 4.45, B 2.86. 1H NMR
4. Experimental
4.1. General
(CD2Cl2):
d
¼ 7.56e7.63 (m, 6H, PPh3), 7.47e7.39 (m, 9H, PPh3), 4.70
All reactions were carried out under argon in anhydrous
solvents which were purified and dried using standard procedures.
The isolation of products was conducted in air. Starting materials
were prepared as described in the literature: CpCo(1,3-C3B2Me5H)
(s, 5H, Cp), 2.54 (s, 6H, 4,5-Me), 1.14 (s, 6H, 1,3-BMe), 0.85 (s, 3H, 2-
Me). 11B{1H} NMR (CD2Cl2):
¼ 0.41 (s).
d
¼ 15.81 (s). 31P{1H} NMR (CD2Cl2):
d
(11) M ¼ Rh; X ¼ Br. Complex 11 was prepared similarly to 9
from complex (0.062 g, 0.06 mmol) and PPh3 (0.032 g,
0.06 mmol). Yield 0.086 (92%). Dark-green solid.
C31H35B2Br2CoRhP (781.86): calcd. C 47.62, H 4.51, B 2.77; found C
47.71, H 4.65, B 2.86. 1H NMR (CDCl3):
[20], [(cod)RhCl]2 [21], [(cod)IrCl]2 [22], [CpCo(
m
-1,3-C3B2Me5)
3
MBr2]2 [13], and [CpCo(
m
-1,3-C3B2Me5)MCl2]2 analogously to the
g
former bromide complexes. The 1H, 11B{1H}, and 31P{1H} NMR
spectra were recorded with a Bruker AMX 400 spectrometer
operating at 400.13, 128.38, and 161.98 MHz, respectively. The IR
spectra of the compounds were measured by Infralum FT-801
d
¼ 7.58e7.68 (m, 6H, PPh3),
7.37e7.43 (m, 6H, PPh3), 7.05e7.15 (m, 3H, PPh3), 4.61 (s, 5H, CpCo),
2.47 (d, 6H, 3JRhH ¼ 0.64 Hz, 4,5-Me),1.20 (d, 6H, 3JRhH ¼ 0.32 Hz,1,3-
(Lumex) FTIR spectrometer over the range 400e4000 cmꢀ1
.
BMe), 0.58 (s, 3H, 2-Me). 11B{1H} NMR (CDCl3):
d
¼ 21.16 (s). 31P{1H}
NMR (CDCl3):
d
¼ 35.04 (d, 1JRhP ¼ 121.6 Hz).
4.2. Synthesis of
4.2.1. CpCo( -1,3-C3B2Me5)MX2(Me2SO)
(12) M ¼ Ir; X ¼ Br. Complex 12 was prepared similarly to 9 from
complex 4 (0.061 g, 0.05 mmol) and PPh3 (0.026 g, 0.1 mmol). Yield
0.075 g (86%). Dark-brown solid. C31H35B2Br2CoIrP (871.17): calcd. C
42.74, H 4.05, B 2.48; found C 42.27, H 3.91, B 2.75. 1H NMR (CDCl3):
m
(5) M ¼ Rh; X ¼ Cl. The Me2SO/CH2Cl2 mixture (20 ml; 1/20) was
added to the solid complex 1 (0.060 g, 0.07 mmol) and stirred for
24 h. The green solution was slowly evaporated to form a black
crystalline precipitate. The product was washed with 3 ml of cooled
CH2Cl2 (0 ꢁC) from excess of Me2SO and dried in vacuum. Yield
0.064 g (91%). Black solid. C15H26B2Cl2CoORhS (508.80): calcd. C
35.41, H 5.15, B 4.25; found C 35.30, H 5.10, B 4.13. 1H NMR (CD2Cl2):
d
¼ 7.60e7.70 (m, 6H, PPh3), 7.47e7.39 (m, 9H, PPh3), 7.14e7.04 (m,
3H, PPh3), 4.65 (s, 5H, Cp), 2.65 (s, 6H, 4,5-Me), 1.24 (s, 6H,1,3-BMe),
0.94 (s, 3H, 2-Me). 11B{1H} NMR (CDCl3):
(CDCl3):
¼ ꢀ1.03 (s).
d
¼ 16.34 (s). 31P{1H} NMR
d
d
¼ 4.88 (s, 5H, CoCp), 2.93 (s, 6H, Me2SO), 2.32 (s, 6H, 4,5-Me), 1.53
(s, 6H, 1,3-BMe), 1.51 (s, 3H, 2-Me). 11B{1H} NMR (CD2Cl2):
¼ 22.29
(bs). IR ( , acetone
, solid sample, KBr, cmꢀ1): 1019 (SO). IR (
solution, KBr, cmꢀ1): 902 (SO).
4.3. X-ray crystallography of 5e12
d
n
n
The crystals suitable for X-ray study were obtained by slow
evaporation of CH2Cl2 from Me2SO/CH2Cl2 solutions (1/20) of
complexes 5e8, slow evaporation of acetone/CH2Cl2 solutions (1/1)
of complexes 9e12 in NMR tube. The principal crystallographic
data and refinement parameters are listed in Tables 1 and 2. X-ray
diffraction experiment was carried out with a Bruker Apex II CCD
area detector, using graphite monochromated Mo Ka radiation
(6) M ¼ Ir; X ¼ Cl. Complex 6 was prepared similarly to 5 from
complex 2 (0.045 g, 0.04 mmol). Yield 0.046 g (90%). Black solid.
C15H26B2Cl2CoIrOS (598.11): calcd. C 30.12, H 4.38, B 3.61; found C
29.73, H 4.36, B 3.45. 1H NMR (CD2Cl2):
d
¼ 4.88 (s, 5H, CoCp), 3.11
(s, 6H, Me2SO), 2.45 (s, 6H, 4,5-Me), 1.56 (s, 6H,1,3-BMe),1.53 (s, 3H,
2-Me). 11B{1H} NMR (CD2Cl2):
¼ 16.09 (bs). IR ( , solid sample, KBr,
cmꢀ1): 1018 (SO). IR ( , acetone solution, KBr, cmꢀ1): 902 (SO).
d
n
(l
¼ 0.71073 Å) at 100 K. Absorption correction was applied semi-
n
empirically using APEX2 program [23]. The structures were
solved by direct methods and refined by the full-matrix least-
squares against F2 in an anisotropic (for non-hydrogen atoms)
approximation. The compounds 5e8 crystallize with two inde-
pendent molecules in the unit cell which are differ from each other
by orientation of the cyclic ligands. The compounds 9e12 crystal-
lize with one CH2Cl2 solvate molecule. All hydrogen atom positions
were refined in isotropic approximation in “riding” model with the
Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to
1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent
thermal parameters of the carbon atoms to which the corre-
sponding H atoms are bonded. All calculations were performed
using the SHELXTL software [24].
(7) M ¼ Rh; X ¼ Br. Complex 7 was prepared similarly to 5 from
complex 3 (0.062 g, 0.06 mmol). Yield 0.067 g (94%). Black solid.
C15H26B2Br2CoORhS (597.70): calcd. C 30.14, H 4.38, B 3.62; found C
30.20, H 4.45, B 3.58. 1H NMR (CD2Cl2):
d
¼ 4.87 (s, 5H, CoCp), 3.07
(s, 6H, Me2SO), 2.42 (s, 6H, 4,5-Me),1.60 (s, 6H,1,3-BMe),1.57 (s, 3H,
2-Me). 11B{1H} NMR (CD2Cl2):
¼ 22.22 (bs). IR ( , solid sample,
KBr, cmꢀ1): 1026 (SO). IR ( , acetone solution, KBr, cmꢀ1): 902 (SO).
d
n
n
(8) M ¼ Ir; X ¼ Br. Complex 8 was prepared similarly to 5 from
complex 4 (0.06 g, 0.05 mmol). Yield 0.063 g (93%). Black solid.
C15H26B2Br2CoIrOS (687.01): calcd. C 26.22, H 3.81, B 3.15; found C
26.35, H 3.97, B 3.12. 1H NMR (CD2Cl2):
d
¼ 4.88 (s, 5H, CoCp), 3.32
(s, 6H, Me2SO), 2.53 (s, 6H, 4,5-Me), 1.63 (s, 6H,1,3-BMe),1.53 (s, 3H,