Dalton Transactions
Paper
Synthesis of compound 5. Compound 1 (0.200 g, 0.5 mmol) C56H82B2F8N6Pd: C, 60.09; H, 7.38; N, 7.51. Found: C, 59.79; H,
and palladium acetate (0.056 g, 0.25 mmol) were taken in a 7.27; N, 7.54. 1H NMR (CDCl3, 500 MHz): δ 1.16 (m, 18H, CH3),
schlenk flask and propanenitrile (20 mL) was added to it. The 1.30 (t, 3H, CH2CH3), 1.49 (d, 6H, CH3), 2.04 (quartet, 2H,
solution was heated at 80 °C for 20 h. A yellow coloured pre- CH3–CH2–CvNH), 2.88 (sept., 2H, CH(CH3)2), 3.53 (sept., 2H,
cipitate was formed and it was filtered. The volatiles were CH(CH3)2), 7.28 (d, 2H, C6H3meta), 7.38 (d, 2H, C6H3meta), 7.44
removed under vacuum and washed with diethyl ether and ((m, 3H, C6H3para + C2–H)). 13C NMR (CDCl3, 125 MHz) δ 23.6,
dried under vacuum to give a yellow coloured residue. Crystals 23.9, 24.9, 25.0, 28.3, 28.4, 126.1, 130.8, 132.4, 132.5, 137.2,
were obtained by slow evaporation of chloroform–ethyl acetate 143.8, 145.9, 146.4, 152.8, 166.3. IR (KBr, cm−1): 3303 (m),
solution of 5 at room temperature. Yield: 0.10 g (68%). Mp: 2966 (s), 2929 (m), 2873 (m), 1659 (vs), 1596 (w), 1464 (m),
208–212 °C (decomp.). Anal. calcd for C28H41Cl2N3Pd: C, 1418 (w), 1388 (w), 1365 (w), 1329 (w), 1299 (m), 1215 (w), 1170
56.33; H, 6.92; N, 7.04. Found: C, 55.80; H, 7.10; N, 7.23. 1H (w), 1133 (m), 1045 (vs), 1032 (vs), 932 (w), 812 (m), 764 (w),
NMR (CDCl3, 500 MHz): δ 1.14–1.29 (m, 21H, CH3 + CH3CH2), 615 (w), 565 (w), 520 (w) cm−1. ESI-MS: calcd 1031.5670,
1.54 (d, 6H, CH3), 1.98 (quartet, 2H, CH3–CH2–CvNH), 2.83 found: 1031.5746 (M − (BF4)−)+.
(sept., 2H, CH(CH3)2), 3.32 (sept., 2H, CH(CH3)2), 7.10 (d, 2H,
Synthesis of compound 8. A schlenk flask was charged with
C6H3meta), 7.20 (t, 1H, C6H3para), 7.27 (s, 1H, C2–H), 7.31 (d, 2H, compound 3 (0.255 g, 0.5 mmol) and palladium acetate
C6H3meta), 7.51 (t, 1H, C6H3para). 13C NMR (CDCl3, 125 MHz): (0.056 g, 0.25 mmol) in 30 mL acetonitrile and was heated at
δ 23.9, 24.0, 24.7, 25.1, 27.4, 28.7, 123.7, 126.0, 128.3, 132.1, 80 °C for 20 hours to give yellow coloured solution. The solu-
133.2, 141.6, 142.6, 146.1, 150.3 (N–HCvN), 160.9 (H2C– tion was filtered through celite and removal of volatiles under
CvNH). IR (KBr, cm−1): 3335 (m), 2964 (vs), 2928 (m), 2870 vacuum and washing with ether and dried under vacuum gave
(w), 1663 (vs), 1595 (w), 1464 (m), 1443 (w), 1408 (w), 1387 (w), yellow residue. Crystals were obtained by slow evaporation of
1364 (w), 1313 (w), 1255 (m), 1214 (w), 1169 (w), 1117 (w), 1059 acetonitrile solution of 8 at room temperature. Yield: 0.241 g
(w), 814 (m), 803 (m), 785 (w), 758 (m), 612 (w), 560 (w), 529 (80%). Mp: 176–180 °C. Anal. Calcd for C54H78F12N6P2Pd: C,
(w), 449 (w) cm−1. ESI-MS calcd for [(M − Cl−) + CH3CN]+: 53.71; H, 6.51; N, 6.96. Found: C, 53.13; H, 6.39; N, 6.59. 1H
601.2289, found: 601.2287.
NMR (CD3CN, 500 MHz): δ 1.17 (m, 18H, CH3) 1.42 (d, 6H,
Synthesis of compound 6. Compound 2 (0.226 g, 0.5 mmol) CH3), 1.93 (s, 3H, CH3–CvNH), 2.64 (sept., 2H, CH(CH3)2),
and palladium acetate (0.056 g, 0.25 mmol) were taken in a 3.19 (sept., 2H, CH(CH3)2), 7.40 (d, 2H, C6H3meta), 7.48 (d, 2H,
schlenk flask and acetonitrile (30 mL) was added to it. The C6H3meta), 7.58 (m, 2H, C6H3para), 8.08 (s, 1H, C2–H). 13C NMR
solution was heated at 80 °C for 20 h. The yellow coloured (CD3CN, 125 MHz): δ 22.9, 23.5, 24.0, 28.3, 28.5, 122.9, 124.0,
solution was filtered through celite and volatiles were removed 125.6, 126.0, 130.7, 132.4, 142.6, 145.6, 153.9, 162.9. IR
under vacuum and washed with diethyl ether and dried under (KBr, cm−1): 3276 (w), 2967 (m), 2930 (w), 2873 (w), 1661 (vs),
vacuum to give a yellow coloured residue. Crystals were 1595 (w), 1462 (m), 1439 (w), 1406 (w), 1389 (w), 1367 (w),
obtained by slow evaporation of acetonitrile solution of 6 at 1328 (w), 1290 (s), 1218 (w), 1165 (w), 1099 (w), 1060 (w),
room temperature. Yield: 0.195 g (72%). Mp: 202–206 °C. Anal. 1043 (w), 935 (w), 842 (vs), 810 (m), 762 (w), 739 (w),
Calcd for C54H78B2F8N6Pd: C, 59.38; H, 7.29; N, 7.69. Found: 684 (w), 618 (w), 594 (w), 557 (m), 530 (w), 464 (w),
1
C, 59.41; H, 7.39; N, 7.74. H NMR (CD3CN, 500 MHz): δ 1.20 440 (w) cm−1. ESI-MS: calcd 1061.4985, found: 1061.4971
(m, 18H, CH3) 1.43 (d, 6H, CH3), 1.65 (s, 3H, CH3–CvNH), (M − (PF6)−)+.
2.72 (sept., 2H, CH(CH3)2), 3.18 (sept., 2H, CH(CH3)2), 7.40 (d,
Synthesis of compound 9. A schlenk flask was charged with
2H, C6H3meta), 7.48 (d, 2H, C6H3meta), 7.58 (m, 2H, C6H3para), compound 3 (0.255 g, 0.5 mmol) and palladium acetate
8.08 (s, 1H, C2–H). 13C NMR (CD3CN, 125 MHz): δ 22.9, 23.5, (0.056 g, 0.25 mmol) in 20 mL propanenitrile and was heated
24.0, 28.3, 28.5, 125.7, 126.1, 130.8, 132.5, 133.0, 136.4, 142.6, at 80 °C for 2 h to give yellow coloured solution. The solution
145.6, 154.0, 163.0. IR (KBr, cm−1): 3300 (m), 2966 (s), 2929 was filtered through celite and removal of volatiles under
(w), 2871 (w), 1662 (vs), 1597 (w), 1463 (w), 1389 (w), 1364 (w), vacuum and washed with mixture of 1 mL THF and 15 mL
1329 (w), 1300 (s), 1217 (w), 1165 (w), 1076 (s), 1051 (vs), ether and dried under vacuum to give yellow residue. Crystals
1036 (s), 932 (w), 812 (w), 764 (w), 731 (w), 626 (w), 568 (w), 521 were obtained by slow evaporation of methanol solution of 9 at
(w), 463 (w) cm−1. ESI-MS: calcd 1003.5409, found: 1003.5414 room temperature. Yield: 0.119 g (40%). Mp: 108–112 °C. Anal.
(M − (BF4)−)+.
Calcd for C56H82F12N6P2Pd: C, 54.43; H, 6.69; N, 6.80. Found:
1
Synthesis of compound 7. Compound 2 (0.226 g, 0.5 mmol) C, 53.93; H, 6.48; N, 6.62. H NMR (CDCl3, 500 MHz): δ 1.11
and palladium acetate (0.056 g, 0.25 mmol) were taken in a (m, 18H, CH3), 1.26 (t, 3H, CH2CH3), 1.46 (d, 6H, CH3), 1.82
schlenk flask and propanenitrile (20 mL) was added to it. The (quartet, 2H, CH3–CH2–CvNH), 2.80 (sept., 2H, CH(CH3)2),
solution was heated at 80 °C for 2 h. The yellow coloured solu- 3.29 (sept., 2H, CH(CH3)2), 7.29 (d, 2H, C6H3meta), 7.39 (d, 2H,
tion was filtered through celite and volatiles were removed C6H3meta), 7.45 (m, 3H, C6H3para + C2–H). 13C NMR (CDCl3,
under vacuum and washed with the mixture of 1 mL THF 125 MHz): δ 23.5, 23.9, 24.9, 25.0, 28.4, 28.5, 124.1, 126.2,
and 15 mL ether and dried under vacuum gave yellow residue. 126.2, 130.9, 132.5, 137.1, 143.7, 146.4, 152.8, 166.5. IR (KBr,
Crystals were obtained by slow evaporation of mixture of cm−1): 3298 (m), 2966 (s), 2930 (m), 2873 (m), 1658 (vs), 1598
chloroform–ethyl acetate solution of 7 at room temperature. (w), 1465 (m), 1388 (w), 1366 (w), 1291 (m), 1215 (w), 1171 (w),
Yield: 0.113 g (41%). Mp: 158–162 °C. Anal. Calcd for 1132 (w), 1059 (m), 879 (vw), 843 (s), 808 (m), 760 (m), 558 (w),
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Dalton Trans.