Full Paper
1
078.20 [M + H]+ expected isotopic profiles. C H Br N N O Pd
NCH ), 2.33–2.12 (m, 10 H, CHCH and NCH CH ), 1.46–1.31 (m, 24
5
4
59
2
2
3
4
2
2
2
2
3
(1080.29): calcd. C 60.04, H 5.50, N 3.89; found C 60.18, H 6.08, N
H, CH CH CH CH ), 1.09 (t, J = 7.5 Hz, 3 H, NCH CH CH ), 0.93 (t,
2
2
2
3
2
2
3
3
1
3
3
.71.
J = 7.0 Hz, 6 H, CH CH ), 0.89 (t, J = 7.2 Hz, 6 H, CH CH ) ppm.
C NMR (100 MHz, CDCl ): δ = 154.97–116.07 (Ar C's), 99.87 (s,
2 3 2 3
3
3
trans-Dibromo-{5-[3-(2,4,6-trimethylphenyl)-imidazol-2-yliden-
-yl]-25,26,27,28-tetrapropyloxycalix[4]arene}pyridine-
OCH O), 99.40 (s, OCH O), 53.96 (s, NCH ), 36.87 (s, CHCH ), 36.56
2
2
2
2
1
(
s, CHCH ), 32.16 (s, CH CH CH ), 30.05 (s, CHCH ), 29.96 (s, CHCH ),
1
2 2 2 3 2 2
palladium(II) (2): Yield 31 % (0.070 g). H NMR (500 MHz, CDCl ):
δ = 8.66 (d, J = 4.5 Hz, 2 H, Ar CH, Py), 7.61 (s, 2 H, Ar CH, mesityl),
3
2
7.71 (s, CHCH CH ), 27.64 (s, CHCH CH ), 23.93 (s, NCH CH ), 22.85
3
2 2 2 2 2 2
(
s, CH CH ), 14.25 (s, CH CH ), 11.59 (s, NCH CH CH ) ppm.
3
3
2 3 2 3 2 2 3
7
.56 (t, J = 7.7 Hz, 1 H, Ar CH, Py), 7.12 (d, J = 1.5 Hz, 1 H, Ar CH,
C H Br N O Pd (1270.53): calcd. C 59.56, H 6.11, N 3.31; found C
63
77
2 3 8
NCHCHN), 7.10–7.08 (m, 2 H, Ar CH, Py), 7.04 (s, 2 H, Ar CH, calix.),
59.47, H 5.98, N 3.17.
3
3
6
.95 (d, J = 1.5 Hz, 1 H, Ar CH, NCHCHN), 6.87 (d, J = 7.5 Hz, 2 H,
3
3
Ar CH, calix.), 6.77 (d, J = 7.5 Hz, 2 H, Ar CH, calix.), 6.71 (t, J =
Typical Procedure for Palladium-Catalysed Suzuki–Miyaura
3
7
.5 Hz, 1 H, Ar CH, calix.), 6.32 (d, J = 7.5 Hz, 2 H, Ar CH, calix.),
Cross-coupling: A 10 mL-Schlenk tube was filled with palladium
3
6
.27 (t, J = 7.5 Hz, 2 H, Ar CH, calix.), 4.52 and 3.31 (AB spin system,
–4
complex (2.5 × 10 mmol, 1 mol-%), aryl chloride (0.25 mmol), aryl-
2
2
J = 13.5 Hz, 4 H, ArCH Ar), 4.46 and 3.16 (AB spin system, J =
2
boronic acid (0.37 mmol), NaH (60 % dispersion in mineral oil;
3
3
13.0 Hz, 4 H, ArCH Ar), 4.04 (t, J = 7.7 Hz, 2 H, OCH ), 3.94 (t, J =
2
2
0.015 g, 0.37 mmol) and decane (0.025 mL, internal reference). 1,4-
7.7 Hz, 2 H, OCH ), 3.79–3.76 (m, 4 H, OCH ), 2.38 (s, 6 H, o-CH -
2
2
3
Dioxane (0.75 mL) was then added. The reaction mixture was
heated at 75 °C. After cooling to room temperature, an aliquot
mesityl), 2.38 (s, 3 H, p-CH -mesityl), 2.03–1.90 (m, 8 H, CH CH ),
3
2
3
3
3
1
0
.06 (t, J = 7.5 Hz, 6 H, CH CH ), 0.99 (t, J = 7.5 Hz, 3 H, CH CH ),
2 3 2 3
(0.5 mL) of the resulting solution was passed through a Millipore
3
13
.95 (t, J = 7.5 Hz, 3 H, CH CH ) ppm. C NMR (125 MHz, CDCl3):
2
3
filter and analysed by GC.
δ = 157.70 (s, Ar CqO), 157.53 (s, Ar CqO), 155.81 (s, Ar CqO), 152.79–
1
3
21.80 (Ar C's), 76.86 (s, OCH ), 76.85 (s, OCH ), 76.66 (s, OCH ),
2 2 2
X-ray Crystallographoc Data: Single crystals of 6·CHCl3 suitable
for X-ray analysis were obtained by slow diffusion of hexane into a
1.12 (s, ArCH Ar), 31.11 (s, ArCH Ar), 23.54 (s, CH CH ), 23.35 (s,
2
2
2
3
CH CH ), 23.28 (s, CH CH ), 21.33 (s, p-CH -mesityl), 20.18 (s, o-CH -
mesityl), 10.74 (s, CH CH ), 10.31 (s, CH CH ), 10.25 (s, CH CH ) ppm.
MS (ESI-TOF): m/z = 1120.24 [M + H] expected isotopic profiles.
C H Br N N O Pd (1122.37): calcd. C 61.00, H 5.84, N 3.74; found
2
3
2
3
3
3
chloroform solution of the imidazolium salt. M = 1000.31; ortho-
r
2
3
2
+
3
2
3
rhombic; space group Pbca; a = 16.6926(3), b = 17.8582(2), c =
3
–3
3
0.7047(5) Å; V = 9749.3(3) Å ; Z = 8; D = 1.363 mg m ; λ(Cu-K ) =
x
α
–1
57
65
2
2
3
4
1.54184 Å; μ = 2.600 mm ; F(000) = 4176; T = 100(2) K. The sample
0.197 × 0.188 × 0.058 mm) was studied with an Oxford Diffraction
C 61.14, H 5.91, N 3.54.
(
SuperNova EOS2 diffractometer. The data collection (2θmax = 67.7°,
omega scan frames via 0.7° omega rotation and 30 s per frame,
range hkl: h –20, 20 k –21, 21 l –40,39) gave 9463 reflections. The
trans-Dibromo-{5-[3-(2,4,6-trimethylphenyl)-imidazol-2-yliden-
1
-yl]-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-
tetrapentylresorcin[4]arene}pyridinepalladium (II) (3): Yield
[
14]
1
structure was solved with SIR-97,
which revealed the non-
4
3 % (0.126 g). H NMR (500 MHz, CDCl ): δ = 8.60–8.58 (m, 2 H, Ar
3
hydrogen atoms of the molecule. After anisotropic refinement, all
the hydrogen atoms were found with a Fourier Difference. The
CH, Py), 7.59–7.54 (m, 1 H, Ar CH, Py), 7.33 (s, 1 H, Ar CH, resorcina-
rene), 7.20 (s, 1 H, Ar CH, resorcinarene), 7.19 (s, 2 H, Ar CH, resorcin-
arene), 7.12–7.08 (m, 2 H, Ar CH, Py), 7.02 (s, 2 H, Ar CH, mesityl),
[
15]
structure was refined with SHELXL-2014
by the full-matrix least-
square techniques [use of F square magnitude; x, y, z, ꢀ for C, Cl,
6
6
5
4
2
.83 (br. s, 1 H, Ar CH, NCHCHN), 6.83 (br. s, 1 H, Ar CH, NCHCHN),
ij
F, N, O and P atoms, x, y, z in riding mode for H atoms; 595 variables
.51 (s, 1 H, Ar CH, resorcinarene), 6.49 (s, 2 H, Ar CH, resorcinarene),
2
2
2
and 7906 observations with I > 2.0σ(I)]; calcd. w = 1/[σ (F ) +
.79 and 4.40 (AB spin system, J = 7.2 Hz, 4 H, OCH O), 5.74 and
o
2
(0.0818P)2 + 4.4884P] where P = (Fo2 + 2F )/3 with the resulting
2
2
3
.47 (AB spin system, J = 6.8 Hz, 4 H, OCH O), 4.94 (t, J = 8.0 Hz,
H, CHCH ), 4.77 (t, J = 8.0 Hz, 2 H, CHCH ), 2.38 (s, 6 H, o-CH -
c
2
–
3
3
R = 0.0533, RW = 0.1419 and SW = 1.051, Δρ < 0.757 e Å .
2
2
3
mesityl), 2.37 (s, 3 H, p-CH -mesityl), 2.33–2.22 (m, 8 H, CHCH ),
3
2
3
Single crystals of 7·CHCl suitable for X-ray analysis were obtained
by slow diffusion of hexane into a chloroform solution of the
3
1
.46–1.31 (m, 24 H, CH CH CH CH ), 0.93 (t, J = 6.8 Hz, 6 H,
2 2 2 3
3
13
CH CH ), 0.89 (t, J = 6.8 Hz, 6 H, CH CH ) ppm. C NMR (100 MHz,
2
3
2
3
imidazolium salt. M = 1046.50; monoclinic; space group P2 ; a =
r
1
CDCl ): δ = 155.03–116.09 (Ar C's), 99.88 (s, OCH O), 99.29 (s,
3
2
9
2
2
.43380(10), b = 18.6628(2), c = 15.1485(2) Å, ꢀ = 100.221(1)°; V =
OCH O), 36.96 (s, CHCH ), 36.58 (s, CHCH ), 32.19 (s, CH CH CH ),
2
2
2
2
2
3
3
–3
624.75(5) Å ; Z = 2; D = 1.324 mg m ; λ(Cu-K ) = 1.54184 Å; μ =
x
α
3
2.17 (s, CH CH CH ), 30.13 (s, CHCH ), 29.96 (s, CHCH ), 27.71 (s,
2 2 3 2 2
–
1
.480 mm ; F(000)
=
1100;
T
=
150(2) K. The sample
CHCH CH ), 22.85 (s, CH CH ), 21.35 (s, p-CH -mesityl), 20.38 (s, o-
2
2
2
3
3
(
0.312 × 0.304 × 0.053 mm) was studied with an Oxford Diffraction
SuperNova EOS2 diffractometer. The data collection (2θmax
1.337°, omega scan frames via 0.7° omega rotation and 30 s per
frame, range hkl: h –11, 11 k –22, 19 l –18,18) gave 9342 reflections.
CH -mesityl), 14.24 (s, CH CH ) ppm. MS (ESI-TOF): m/z = 1268.44
3
2
3
+
+
=
[
M – Py] , 1228.43 [M – Br – Py + MeCN] expected isotopic profiles.
7
C H Br N O Pd (1346.62): calcd. C 61.54, H 6.06, N 3.12; found C
69
81
2 3 8
6
1.66, H 6.19, N 2.98.
[
14]
The structure was solved with SIR-97,
which revealed the non-
trans-Dibromo-[5-(3-propylimidazol-2-yliden-1-yl)-4(24),6(10),
hydrogen atoms of the molecule. After anisotropic refinement, all
1
2(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylre-
the hydrogen atoms are found with a Fourier Difference. The whole
1
[15]
sorcin[4]arene]pyridinepalladium(II) (4): Yield 51 % (0.130 g). H
structure was refined with SHELXL-2014
by the full-matrix least-
NMR (500 MHz, CDCl ): δ = 8.85–8.82 (m, 2 H, Ar CH, Py), 7.67 (tt,
square techniques [use of F square magnitude; x, y, z, ꢀ for C, Cl,
3
ij
3
4
J = 7.5, J = 1.5 Hz, 1 H, Ar CH, Py), 7.30 (s, 1 H, Ar CH, resorcin-
F, N, O and S atoms, x, y, z in riding mode for H atoms; 634 variables
2
2
arene), 7.25–7.20 (m, 2 H, Ar CH, Py), 7.19 (s, 1 H, Ar CH, resorcin-
and 9134 observations with I > 2.0σ(I)]; calcd. w = 1/[σ (F ) +
o
3
(0.0799P)2 + 0.8441P] where P = (Fo2 + 2F )/3 with the resulting
2
arene), 7.17 (s, 2 H, Ar CH, resorcinarene), 7.01 (d, J = 1.5 Hz, 1 H,
c
3
–3
Ar CH, NCHCHN), 6.68 (d, J = 1.5 Hz, 1 H, Ar CH, NCHCHN), 6.49 (s,
R = 0.043, RW = 0.1209 and SW = 1.036, Δρ < 0.565 e Å .
1
H, Ar CH, resorcinarene), 6.48 (s, 2 H, Ar CH, resorcinarene), 5.78
2
and 4.38 (AB spin system, J = 7.2 Hz, 4 H, OCH O), 5.70 and 4.38
CCDC 1058184 (for 6) and 1057661 (for 7) contain the supplemen-
2
2
3
(AB spin system, J = 7.0 Hz, 4 H, OCH O), 4.90 (t, J = 8.0 Hz, 2 H,
2
3
3
CHCH ), 4.75 (t, J = 8.0 Hz, 2 H, CHCH ), 4.63 (t, J = 7.5 Hz, 2 H,
2
2
Eur. J. Inorg. Chem. 2016, 1115–1120
www.eurjic.org
1119
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim