E. Amadio et al. / Journal of Organometallic Chemistry 716 (2012) 193e200
195
1
3
1
C{ H} NMR (75.5 MHz, 298 K, acetone-d
6
):
d
155.3, 152.0,
collection by leastesquares refinement of all reflection positions.
Two reference frames were collected after every 50 frames in order
to assess crystal stability. No systematic change was noticed neither
in peak positions nor in intensities.
1
49.7, 141.1, 127.0, 126.1, 125.7, 120.6, 63.7, 54.1, 27.1, 22.1, 13.0.
MS(ESI, CH
ꢀ
þ
3
CN; m/z, %): 1660 (1) [4M ꢀ BF
4
] , 1222 (2)
ꢀ
þ
ꢀ þ
ꢀ þ
[
(
3M ꢀ BF
4
] , 786 (8) [2M ꢀ BF
4
] , 349.05 (100) [M ꢀ BF
4
] , 321.06
ꢀ
þ
10) [M ꢀ BF
4
ꢀ C
2
H
4
] .
The structure was solved by heavyeatom methods using
C
14
H19BF
4
N
4
Pd (436.5): calc. C, 38.52; H, 4.39; N, 12.83; found C,
SHELXS [22] and refined by full-matrix leastesquares methods
2
3
8.72; H, 4.43; N, 12.90.
based on F
o
with SHELXL-97 [22] in the framework of OLEX2 [23]
software. During the refinement, some peaks appeared in posi-
tions compatible with a second arrangement of both the ligand
alkyl chain and the tetrafluoroborate anion. In either case, a satis-
factory model was obtained by assuming the involved atoms (C3,
C4, C5 and F2, F3, F4, respectively) disordered over two sites, the
occupancies of which were constrained to sum to 1.0; however, the
final data completeness (0.917) was hampered by disorder. In the
last cycles of refinement, non-hydrogen atoms were refined
anisotropically, with the exception of the disordered atoms of the
tetrafluoroborate anion. Hydrogen atoms were included in ideal-
ized positions and refined with a ‘riding’ model. The Uiso values of
hydrogen atoms were calculated from the Ueq of the pertinent
parent atom. Main crystallographic data are listed in Table 1;
selected bond lengths and angles are listed in Table 2.
2
.3. [Pd( 3
h
-C
3
H
5
)(2-((4-propyl-1H-1,2,3-triazol-1-yl)methyl)
pyridine)](ClO
4
) (3)
Complex 3 was prepared analogously to complex 2 but using
AgClO
4
instead of AgBF
4
. Yield: 80%. The NMR spectroscopic data
ꢀ1
2
ꢀ1
are identical to those of complex 2. L
M
¼ 159
U
cm mol
ꢀ
3
(
1 ꢂ 10 M in acetone).
ꢀ
þ
MS(ESI, CH
3
CN; m/z, %): 1247 (4) [3M ꢀ ClO
4
] , 797 (8)
ꢀ
þ
ꢀ þ
4
[
[
2M
M ꢀ ClO
19ClN
C, 37.40; H, 4.37; N, 12.64.
ꢀ
ClO
4
] , 349.03 (100) [M
ꢀ
ClO ] , 321.10 (11)
ꢀ
þ
4
ꢀ C
2
H
4
] .
C
14
H
4 4
O Pd (449.2): calc. C, 37.43; H, 4.26; N, 12.47; found
2
.4. [Pd( 3
methyl)pyridine)](BF
h
-2-CH
3
-C
3
H
4
)(2-((4-propyl-1H-1,2,3-triazol-1-yl)
Full listings of atomic coordinates, bond lengths and angles,
anisotropic thermal parameters are available as Supporting
information as .cif file (see below).
4
) (4)
Complex 4 was prepared analogously to complex 2 by reacting
3
[
L
PdCl(
h
-2-CH
U
3
-C
3
H
4
)]
2
with L2. White crystals Yield: 85%.
2
.6. Catalytic experiments
ꢀ1
2
ꢀ1
ꢀ3
M
¼ 138
cm mol (1 ꢂ 10 M in acetone).
1
H NMR (300 MHz, 298 K, acetone-d
6
):
d
9.04 (d, J ¼ 5.1 Hz, 1H),
The reactions were carried out under an inert atmosphere
8
(
2
.36 (s, 1H), 8.24 (td, J ¼ 7.7, 1.6 Hz, 1H), 8.04 (d, J ¼ 7.6 Hz, 1H), 7.71
(argon). In a typical catalytic run, the aryl halide (4.0 mmol), phe-
t, J ¼ 6.3 Hz, 1H), 6.04 (br s, 2H), 4.29 (s, 2H, syn), 3.55 (s, 2H, anti),
nylboronic acid (6.0 mmol), potassium carbonate (8.0 mmol) were
introduced in a glass reactor (volume: 50 mL) and diluted in 12 mL
of amine free dimethylformamide containing 5% (v/v) of H O. To
2
the resulting suspension n-undecane (1.0 mmol, internal standard)
and finally the appropriate amount of complex 2 were added. The
reaction mixture was heated under stirring at 110 C for 2 h, then,
after cooling to room temperature, filtered over a short plug of
celite and analyzed by GLC. The coupling products were identified
by their GCeMS and H NMR spectra.
.73 (t, J ¼ 7.6 Hz, 2H), 1.68 (m, 2H), 0.95 (t, J ¼ 7.4 Hz, 3H).
1
H NMR (300 MHz, 223 K, acetone-d
6
): d 9.07 (d, 1H), 8.40 (s,
1
H), 8.28 (td, J ¼ 7.7, 1.6 Hz, 1H), 8.02 (d, J ¼ 7.6 Hz, 1H), 7.75 (t,
J ¼ 6.3 Hz, 1H), 6.18 (d, J ¼ 15.1 Hz, 1H) 5.96 (d, J ¼ 15.1 Hz, 1H), 4.31
(
(
s, 1H, syn), 4.24 (s, 1H, syn), 3.59 (s, 1H, anti), 3.48 (s, 1H, anti), 2.68
ꢁ
t, 2H), 1.61 (m, 2H), 0.90 (t, 3H).
13
1
6
C{ H} NMR (75.5 MHz, 298 K, acetone-d ): 151.9, 149.6, 141.0,
1
37.0, 126.9, 126.0, 125.5, 62.3, 54.1, 27.1, 22.5, 22.2, 12.9.
MS(ESI, CH
1
ꢀ
þ
3
CN; m/z, %): 1715 (12) [4M ꢀ BF
4
] , 1262 (16)
ꢀ
þ
ꢀ þ
ꢀ þ
4
] ,
[
3
3M ꢀ BF
4
] , 815 (14) [2M ꢀ BF
4
] , 363.07 (100) [M ꢀ BF
ꢀ
þ
35.05 (9) [M ꢀ BF
4
ꢀ C
2
H
4
] .
Table 1
C
15
H21BF
4
N
4
Pd (450.58): calc. C, 39.98; H, 4.70; N, 12.43; found
Crystallographic data for the complex 2.
C, 40.18; H, 4.55; N, 12.31.
Empirical formula
Formula weight
Wavelength (A)/temperature (K)
Crystal system
Crystal size
14 19 4 4
C H N BF Pd
436.54
0.71070/300(1)
Triclinic
ꢀ
2.5. X-ray analysis
Crystals of the complex [Pd(h3-C
triazol-1-yl)methyl)pyridine)](BF
0.35 ꢂ 0.25 ꢂ 0.20
P ꢀ 1 (no. 2)
9.0759(3)
9.2046(3)
11.9407(5)
96.349(3)
105.874(3)
112.877(3)
857.12(5)
2
1.691
1.126
436.0
16,237
4254/0.048
4254
3 5
H )(2-((4-propyl-1H-1,2,3-
), suitable for the X-ray experi-
Space group
4
a (A)
ꢀ
ꢀ
ment, were grown by slow diffusion of diethyl ether into an acetone
solution. A specimen coated with paratone oil was sticked on
a Lindemann glass capillary and mounted on the goniometer head
of an Oxford Diffraction/Agilent Gemini E diffractometer, equipped
with a 2K ꢂ 2K EOS CCD area detector and sealed-tube Enhance
b (A)
ꢀ
c (A)
a
b
g
(deg)
(deg)
(deg)
Volume ( ꢀA )
3
(
Mo) and (Cu) X-ray sources. Data were collected with the
u
-scans
Z (molecules/unit cell)
Calculated density (Mg mꢀ3)
technique at room temperature, with graphite-monochromated
Absorption coefficient,
F(000)
Total reflections
m
(mmꢀ1)
ꢀ
Mo K
a
(l
¼ 0.71070 A) radiation, in a 1024 ꢂ 1024 pixel mode,
using 2 ꢂ 2 pixel binning.
A total of 1774 frames in sixteen runs were measured with a step
Independent (unique) reflections/Rint
ꢁ
Observed reflections [I > 2
Data/parameters/restraints
Goodness-of-fit on F2
s(I)]
of 0.5 . The diffraction intensities were corrected for Lorentz and
5106/245/386
1.032
polarization effects, and were also corrected with respect to
absorption. Empirical multi-scan absorption corrections using
equivalent reflections were performed with the scaling algorithm
SCALE3 ABSPACK. Data collection, data reduction and finalization
were carried out through the CrysAlis Pro software [21]. Accurate
unit cell parameters were determined during the whole data
a
b
c
Final R indices [I > 2
s
(I)]
R
1
¼ 0.0509; wR
2
¼ 0.1402
Largest difference peak and hole (e ꢀA ꢀ3)
1.100 and ꢀ1.220
P
a
b
c
Goodness-of-fit ¼ [ (w (F2
2
)2/(Nobsevns ꢀ Nparams)]1/2, based on all data.
o
ꢀ F
c
P
P
R
1
¼
(jF
o
j ꢀ jF
c
j)/ jF
o
j.
P
P
2
2
) ]/ [w (F2
2
)2]]1/2.
wR
2
¼ [ [w (F
o
ꢀ F
c
o