120
A. Mohan et al. / Journal of Organometallic Chemistry 799-800 (2015) 115e121
22.2,22.1,20.3, 20.2; ESI-MS: HRMS calc. for C38H54N6PdI [MꢀI]þ:
solvent was evaporated to give 0.59 g of complex 13 in 80% yield.
Single crystals were grown from a mixture of dichloromethane and
827.2489, found: 827.2505.
hexane (4:1, v/v).
25
4.2. Synthesis of complex 11
Complex 13: mp: 186e188 ꢁC (decomposed); [
a]
¼ ꢀ1.2 (c 0.5,
D
CH2Cl2); IR (KBr pellet, cmꢀ1) 2927, 2865,1449,1331,1071, 762, 696;
Triazolium iodide 9 (1.05 g, 2.5 mmol) was dissolved in 25 mL
dichloromethane to give a yellow solution. The solution turned to
dark brown on addition of palladium acetate (0.34 g, 1.5 mmol). The
reaction mixture was stirred at room temperature for 72 h during
which the colour turned yellow. The reaction mixture was filtered
and solvent was evaporated to get 11 (1.12 g, 1.17 mmol) in 95%
yield. Complex 11 was crystallized from DCM: hexane (2:1, v/v) to
1H NMR (500 MHz, CDCl3)
d
8.88e8.89 (m, 2H), 7.94e7.95 (m, 2H),
7.64 (t, J ¼ 7 Hz,1H), 7.56 (t, J ¼ 7 Hz, 2H), 7.53 (t, J ¼ 7 Hz, 1H),
7.22e7.24 (m, 2H), 5.22e5.25 (m, 1H), 3.97 (s, 3H), 2.87e2.90 (m,
1H), 2.06e2.08 (m, 1H), 1.82e1.90 (m,2H), 1.75e1.79 (m, 1H),
1.63e1.73 (m, 1H), 1.31e1.43 (m, 2H), 1.12 (d, J ¼ 7.0 Hz, 3H),
1.03e1.08 (m, 1H), 0.98 (d, J ¼ 6 Hz, 3H), 0.92 (d, J ¼ 7 Hz, 3H); 13
C
NMR (125 MHz, CDCl3)
d 154.0, 143.7, 137.3, 133.8, 130.8, 129.9,
give single crystals suitable for X-ray crystallography.
128.6, 128.2, 124.3, 67.7, 47.7, 43.1, 37.8, 34.4, 32.1, 29.8, 25.7, 24.2,
22.3, 21.8, 19.3; ESI-MS: HRMS: m/z calcd for (MꢀI) C24H32N4PdI
609.0706, found 609.0705.
25
Complex 11: mp: 260e264 ꢁC (decomposes); [
a
]
¼ ꢀ54.8ꢁ (c
D
0.5, CH2Cl2); IR (KBr pellet, cmꢀ1).3056, 2945, 2869, 1453, 1384,
1325, 1070, 766, 697; 1H NMR (500 MHz, CDCl3)
d 7.86e7.89 (m,
2H), 7.69e7.71 (m, 2H), 7.44e7.50 (m, 3H), 7.39e7.41 (m, 1H), 7.30
(t, J ¼ 7 Hz, 2H), 5.14e5.20 (m, 1H), 4.75e4.81 (m, 1H), 3.87 (s, 3H),
3.88 (s, 3H), 2.95 (t, J ¼ 6 Hz, 2H), 2.09e2.12 (m, 1H), 1.94e2.0 (m,
1H),1.85e1.91 (m, 1H),1.75e1.85 (m, 3H),1.6e1.7 (m, 1H),1.47e1.54
(m, 2H), 1.11e1.18 (m, 1H), 1.08 (d, J ¼ 7.0 Hz, 4H), 1.00e1.06 (m, 2H)
0.91e0.96 (m, 12H), 0.79 (d, J ¼ 7.0 Hz, 3H), 0.49 (d, J ¼ 7 Hz, 3H);
Acknowledgements
Research grant from DST (SR/S1/OC-61/2011), New Delhi is
gratefully acknowledged. We thank Department of Chemistry, IIT
Madras for infrastructure facilities.
13C NMR (125 MHz, CDCl3)
d 156.4, 155.9144.6, 144.3, 131.0, 130.7,
Appendix A. Supplementary material
129.3, 129.1, 128.7, 128.6, 128.5, 128.4, 67.0, 66.8, 47.4, 47.3, 43.6,
43.3, 37.3, 37.0, 34.6, 34.5, 32.4, 32.2, 25.6, 25.3, 24.5, 24.3, 22.4,
22.2, 21.9, 21.8, 19.7, 18.9; ESI-MS: HRMS: m/z calcd for (MꢀI)
CCDC numbers 1029252e1029257 contain the supplementary
crystallographic data for compounds 4, 10, 12, 13, 5, and 11
respectively. These data can be obtained free of charge from The
C
38H54N6PdI 827.2489, found 827.2488.
4.3. Synthesis of complex 12
Triazolium iodide 5 (0.419 g, 1 mmol) was dissolved in pyridine
(5 mL) under nitrogen atmosphere. Potassium iodide (0.18 g,
1 mmol) and potassium carbonate (0.65 g, 5 mmol) were added
followed by palladium acetate (0.224 g, 1 mmol). The reaction
mixture was stirred at 80 ꢁC under nitrogen atmosphere. After 24 h
the reaction was cooled and 20 mL dichloromethane was added.
The reaction mixture was filtered and the residue was washed with
dichloromethane (2 ꢂ 20 mL). The filtrate was dried over sodium
sulphate and solvent was evaporated to give complex 12 (0.65 g) in
86% yield. Single crystals suitable for X-ray diffraction were grown
Appendix B. Supplementary data
Supplementary data related to this article can be found at http://
References
from chloroform and hexane (4:1, v/v) by slow evaporation.
25
Complex 12: mp:160e162 ꢁC (decomposed). [
a]
¼ þ3.1ꢁ (c 0.5,
D
CH2Cl2); IR (KBr pellet, cmꢀ1) 2947, 2861, 1450, 1332, 1178, 1073,
761, 693; 1H NMR (500 MHz, CDCl3)
d
8.88 (dd, J ¼ 2 Hz,
J ¼ 5 Hz,2H), 7.95 (dd, J ¼ 2 Hz, J ¼ 5 Hz, 2H), 7.65 (tt, J ¼ 7 Hz,1H)
7.56 (t, J ¼ 7 Hz,2H), 7.53 (t, J ¼ 7 Hz,1H), 7.21e7.24 (m, 2H), 5.79 (q,
J ¼ 3 Hz, 1H), 3.98 (s, 3H), 3.18e3.22 (m, 1H), 1.96e2.12 (m, 2H),
1.90e1.94 (m, 1H), 1.75e1.79 (m, 2H), 1.59e1.66 (m, 1H), 1.40e1.48
(m, 1H), 1.14 (d, J ¼ 7 Hz, 3H),1.06e1.09 (m, 1H), 0.92 (d, J ¼ 7 Hz,
€
[9] O. Kühl, Functionalised in N-Heterocyclic Carbene Complexes, John Wiley &
Sons, ch. 5, pp. 279e308.
3H), 0.72 (d, J ¼ 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d 153.9,
143.4, 137.3, 134.2, 130.9, 129.9, 128.6, 128.2, 124.3, 65.1, 48.0, 39.8,
37.8, 35.2, 28.9, 25.9, 24.4, 23.7, 22.1, 20.2; ESI-MS: m/z 609.0706
(MꢀI) HRMS: m/z calculated for C24H32N4PdI 609.0706, found
609.0720.
4.4. Synthesis of complex 13
Triazolium iodide 9 (0.42 g, 1 mmol) was dissolved in pyridine
(5 mL) under nitrogen atmosphere. Potassium iodide (0.18 g,
1 mmol) and potassium carbonate (0.65 g, 5 mmol) were added
followed by palladium acetate (0.224 g, 1 mmol). The reaction
mixture was stirred at 80 ꢁC. After 24 h the reaction was cooled and
20 mL dichloromethane was added. The reaction mixture was
filtered and the residue was washed with dichloromethane
(2 ꢂ 20 mL). The filtrate was dried over sodium sulphate and
€