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E. Silarska et al. / Applied Catalysis A: General 466 (2013) 216–223
4.2. General procedure for the Suzuki–Miyaura coupling of aryl
chlorides
J(H,H) = 7.1 Hz, 8H, N CH2); 2.55 (t, J(H,H) = 7.3 Hz, 8H, CH2 CN);
2.24 (m, J(H,H) = 7.1 Hz 8H, CH2); 13C NMR (125.75 MHz, CD3CN,
25 ◦C, TMS): ı = 142.0 (N CH N); 122.5 (CH CH); 119.2 (CN); 48.0
(N CH2); 25.0 (CH2); 13.5 (CH2).
[dmdim][PdCl4]: The complex was obtained according to the pro-
cedure given for [HIPr]2[PdCl4] using 0.4 g (1.4 mmol) of PdCl2(cod)
and 0.4 g (1.4 mmol) of [dmdim]Cl; yield: 95%; elemental analysis
calcd. (%). PdCl4C15H26N4O2: C 33.18, H 4.83, N 10.32; found: C
33.40, H 4.91, N 10.33. 1H NMR(500 MHz, CD3CN, 25 ◦C, TMS) ı = 7
78 (s, 2H, CH ); 7.61 (s, 2H, CH); 5.54 (s, 4H, CH2 O); 3.77 (s, 6H,
CH3 N); 3.42 (t, J(H,H) = 6.5, 4H, CH2 O); 2.53 (s, 6H, –CH3); 1.70
(m, J(H,H) = 6.5, 2H, –CH2–); 13C NMR (125.75 MHz, CD3CN, 25 ◦C,
In a 50 mL Schlenk tube phenylboronic acid (1.0 mmol) was
mixed with aryl chloride (1.0 mmol). Then base (1.2 mmol), palla-
dium complex (0.01 mmol) and 2-propanol (5 mL) were added. The
Schlenk tube was placed in an 70 ◦C oil bath and stirred for 24 h. The
mixture was then cooled to room temperature. The organic prod-
ucts were extracted with 10 mL of n-hexane (15 min with stirring).
For better phase separation, 1 mL of water was added and the upper
n-hexane layer was taken for GC analysis.
4.3. General procedure for Hg(0) test
TMS): ı = 146 0 (N C N); 123.4 (C C); 122.5 (C C); 77.0 (CH2 O);
66.8 (N CH3); 35.5 (O CH2); 27.3 (CH2); 10.1 (CH3).
The Suzuki–Miyaura reaction was carried out in a 50 mL Schlenk
tube. The base (1.2 mmol) and the palladium complex (0.01 mmol)
were weighted and placed in the Schlenk tube. Next, 5 mL of 2-
propanol and 6.25 mmol of Hg(0) were added. The reactor was
closed with a rubber plug and the reaction mixture was stirred
at 40 ◦C. After the specified reaction time, phenylboronic acid
(1.5 mmol, 0.184 g) and 2-bromotoluene (1.0 mmol) were added to
the Schlenk tube and the mixture was stirred at 40 ◦C. After 2 h, the
reactor was cooled down and the organic products were extracted
with 10 mL of n-hexane. The organic products were analyzed using
the GC–MS method.
[mdim][PdCl4]: The complex was obtained according to the pro-
cedure given for [HIPr]2[PdCl4] using 0.4 g (1.4 mmol) of PdCl2(cod)
and 0.4 g (1.4 mmol) of [mdim]Cl; yield: 90%; elemental analysis
calcd. (%). PdCl4C13H22N4O2: C 30.40, H 4.21, N 10.76; found: C
30.34, H 4.31, N 10.89. 1H NMR(500 MHz, CD3CN, 25 ◦C, TMS) ı = 9
62 (s, 2H, –CH ); 7.90 (s, 2H, –CH ); 7.85 (s, 2H, –CH ); 5.64 (s, 4H,
–CH2 O); 3.92 (s, 6H, –CH3); 3.63 (t, J(H,H) = 6.5, 4H, –CH2 ); 1.80
(t, J(H,H) = 6.5, 2H, –CH2 ); 13C NMR (125.7 5 MHz, CD3CN, 25 ◦C,
TMS): ı = 138.0 (N
C N); 124.3 (C C); 122.2 (C C); 79.3 (CH2 O);
66.5 (N CH3); 36.2 (O CH2); 29.0 (CH2).
4.5. Measurements
4.4. Synthesis of palladium complexes:
1H and 13C NMR spectra were measured in CD3CN and C6D6
on Bruker 500 spectrometers. Morphology and microstructure
were investigated by TEM (Philips CM-20 SuperTwin operating at
200 kV and providing 0.25 nm resolution). The products of the cat-
alytic experiments were analyzed with a GC–MS (Hewlett Packard
8452A instrument). Experiments with microwaves heating were
performed in microwave oven (Plazmatronika RM-800, 256 W).
[HIPr]2[PdCl4]: 0.45 g (1.0 mmol) of [HIPr]Cl was added to the
solution of 0.14 g (0.48 mmol) PdCl2(cod) in hot CH3CN (5 mL). The
mixture was heated for 15 min, until the yellow solution became
red. The solution was cooled to room temperature and solvent
was removed under reduced pressure. The product was precip-
itated by addition of diethyl ether (2–3 mL). Product yield: 85%;
elemental analysis calcd. (%) for PdCl4C54H78N4: C 62.88, H 7.62,
N 5.46; found: C 62.37, H 7.46, N 5.40. 1H NMR(500 MHz, CD3CN,
25 ◦C, TMS): ı = 8.49 (s, 2H, N CH N); 7.57 (t, J(H,H) = 7.8 Hz, 4H,
Ar); 7.42 (d, J(H,H) = 7.8 Hz, 8H, Ar); 4.48 (s, 8H, CH2 CH2); 3.10
(m, J(H,H) = 6.9 Hz, 8H, CH); 1.40 (d, J(H,H) = 6.9 Hz, 24H, CH3); 1.26
(d, J(H,H) = 6.9 Hz, 24H, CH3,); 13C NMR (125.75 MHz, CD3CN, 25 ◦C,
TMS): ı = 160.0 (N CH N); 147.2 (Ar); 131.0 (Ar); 125.5 (Ar); 53.7
(CH2 CH2); 28.5 (CH); 24.0 (CH3); 23.5 (CH3).
[HIMes]2[PdCl4]: The complex was obtained according to the
procedure given for [HIPr]2[PdCl4] using 0.3 g (1.0 mmol) of
PdCl2(cod) and 0.72 g (2.1 mmol) of [HIMes]Cl; yield: 87%; elemen-
tal analysis calcd. (%) for PdCl4C42H50N4: C 58.72, H 5.87, N 6.52;
found: C 58.20, H 5.44, N 6.38. 1H NMR(500 MHz, CD3CN, 25 ◦C,
TMS): ı = 8.94 (s, 2H, N CH N); 7.75 (s, 4H, CH CH); 7.19 (s, 8H,
Ar); 2.40 (s, 12H, CH3); 2.16 (s, 24H, CH3); 13C NMR (125.75 MHz,
CD3CN, 25 ◦C, TMS): ı = 141.0 (N CH N); 134.0 (Ar); 129.6 (Ar);
125.6 (CH CH); 20.0 (CH3); 16.0 (CH3).
Acknowledgments
Financial support of National Science Foundation (NCN) with
grant 2012/05/B/ST5/00265 is gratefully acknowledged (AMT, ES).
The authors thank Andrea Perez-Cossio Arias (Complutense
University of Madrid) for carrying out microwaves experiments,
Tomasz Pac´kowski (Faculty of Chemistry, University of Wrocław)
for synthesis of [dmdim][PdCL4] and [mdim][PdCl4] complexes,
Marek Hojniak, M.Sc. (Faculty of Chemistry, University of Wrocław)
for preparing the GC–MS analyses and Wojciech Gil, Ph.D. (Faculty
of Chemistry, University of Wrocław) for TEM analyses.
References
[HSIMes]2[PdCl4]: The complex was obtained according to the
procedure given for [HIPr]2[PdCl4] using 0.17 g (0.6 mmol) of
PdCl2(cod) and 0.4 g (1.2 mmol) of [HSIMes]Cl; yield: 48%; ele-
mental analysis calcd. (%). for PdCl4C42H54N4: C 58.44, H 6.31, N
6.49; found: C 58.43, H 6.65, N 6.10. 1H NMR(500 MHz, CD3CN,
25 ◦C, TMS) ı = 8.18 (s, 2H, N CH N); 6.99 (s, 8H, Ar); 4.33 (s,
8H, CH2 CH2); 2.26 (s, 24H, CH3); 2.23 (s, 12H, CH3); 13C NMR
(125.75 MHz, CD3CN, 25 ◦C, TMS): ı = 159.8 (N CH N); 135.3 (Ar);
129.5 (Ar); 51.0 (CH2 CH2); 20.0 (CH3); 16.6 (CH3).
[bcpim]2[PdCl4]: The complex was obtained according to the
procedure given for [HIPr]2[PdCl4] using 0.32 g (1.1 mmol) of
PdCl2(cod) and 0.5 g (2.2 mmol) of [bcpim]Cl; yield: 78%; elemen-
tal analysis calcd. (%). PdCl4C22H30N4: C 40.43, H 4.66, N 17.13;
found: C 39.81, H 4.12, N 17.03. 1H NMR(500 MHz, CD3CN, 25 ◦C,
TMS) ı = 9.96 (s, 2H, N CH N); 7.49 (s, 4H, CH CH); 4.32 (t,