3916
P.B. Kraikivskii et al. / Journal of Organometallic Chemistry 694 (2009) 3912–3917
MS (70 eV): m/z (%) = 39(65.7), 50.0(51.4), 51(50.4), 63(61.2),
53.61(C17), 28.44(C18), 26.16(C19), 26.34(C20), 28.30(C21),
24.49(C22), 25.16(C23), 37.65(C24), 132.44(C25), 119.48(C26),
29.09(C27), 24.14(C28), 24.23(C29), 29.29(C30), 24.42(C31),
24.57(C32) ppm (Fig. 3).
180(100.0), 193(58.9), 207(36.7), 221(42.8).
IR (KBr) cmꢀ1: 3401(w), 3023(m), 2823(m), 1620(s), 1548(s),
1569(s), 1531(s), 1506(s), 1468(s), 1447(s), 1420 (s), 1405(s),
1390(s), 1362(s), 1316(s), 1236(s), 1198(s), 1122(s), 989(vs),
906(s), 844(s), 830(s), 812(s), 795(s), 770(s), 728(d), 686(s),
636(s), 238(Ni–N, w).
3.6. Synthesis of 4
(a) A solution of complex 3 (2.58 g, 5 mmol) in 100 ml of diethyl
ether was kept in a Schlenk flask at 20–25 °C for 5 h and then
evaporated to give a reddish-brown powder. This was dis-
solved in 50 ml of pentane and kept in a refrigerator at
ꢀ30 °C for five days to obtain an amorphous reddish-brown
precipitate which was filtered off and dried for 6 h at 10ꢀ2
mbar, 20 °C. The product is stable in argon but air-sensitive.
Yield 1.99 g (3.85 mmol), 77%. m.p. 97– 100 °C 60 – 65 °C. Anal.
Calc. for C32H46N2Ni (517.41): C, 74.28; H, 8.96; N, 5.41; Ni,
11.34. Found: C, 73.42; H, 8.05; N, 4.70%. MS (70 eV): m/z
(%) = 31(12.1), 41(29.8), 59(18.8), 74(30.0), 186(13.56),
228(43.4), 418(32.4), 434(40.7), 476(100.0), 516(65.2).IR
(KBr) cmꢀ1: 3052(m), 3012(s), 2960(s), 2923(s), 2865(s),
2740(m), 2688(s), 1932(s), 1913(s), 1872(s), 1847(s), 1812(s),
1783(s), 1762(s), 1641(N@C, s), 1490(s), 1384(d), 1313(vs),
1253(s), 1218(s), 1205(s), 1076(vs), 987(vs), 919(s), 873(s),
794(s), 754(d), 568(s), 532(s).1H NMR (500 MHz, [D8]THF,
297 K): d = 6.94 (m, 1H, CH3), 6.84 (m, 1H, CH4), 6.97(m, 1H,
CH5), 4.57(d, 2JHH = 24.81 Hz, 1H, CH27), 4.78 (d,
2JHH = 25.24 Hz, 1H, CH27’), 7.18 (m, 3H,CH11–CH13), 1.43 (d,
3.5. Synthesis of 3
A cold solution (ꢀ5 °C) of (2,6-diisopropylphenyl)diazabutadi-
ene (1.50 g, 4 mmol) in 100 ml of diethyl ether was slowly, during
30 min, added by drops to a vigorously stirred solution of Ni(allyl)2
(0.564 g, 4 mmol) in 100 ml of diethyl ether keeping the tempera-
ture at ꢀ5 °C. The resulting bright red reaction mixture was kept at
this temperature for another 2 h followed by filtration. The filtrate
was evaporated to give a bright red powder. This was dissolved in
50 ml of pentane at ꢀ5 °C. The solution was kept in a refrigerator at
ꢀ30 °C for five days to obtain a crystalline precipitate as thin bright
red plates. The crystals were filtered off at ꢀ30 °C and dried in vac-
uum for 6 h at 10ꢀ2 mbar, 20 °C). The product is stable in argon but
air-sensitive.
Yield 1.07 g (2.08 mmol), 52%.
Decomp. 60 – 65 °C. Anal. Calc. for C32H46N2Ni (517.41): C,
74.28; H, 8.96; N, 5.41; Ni, 11.34. Found: C, 75.16; H, 8.20; N, 4.92%.
HRMS: C32H46N2Ni calculated
– 516.3014, measured –
516.29939 (ꢀ2 mmu).
MS (70 eV): m/z (%) = 41(24.9), 59(13.9), 186(13.0), 228(43.2),
418(33.4), 434(42.9), 476(100.0), 516(74.8).
2
2JHH = 13.8 Hz, 1H, CH215), 1.59 (d, JHH = 6.25 Hz, 1H,
2
CH215’), 5.35(m, 1H, CH16), 1.41 (d, JHH = 8.89 Hz, 1H,
IR (KBr) cmꢀ1: 3052(m), 3012(s), 2960(s), 2923(s), 2865(s),
2740(m), 2688(s), 1932(s), 1913(s), 1872(s), 1847(s), 1812(s),
1783(s), 1762(s), 1602(N@C,s) 1571(s), 1461(d), 1363(s), 1355(s),
1313(vs), 1253(s), 1105(s), 1076(vs), 987(vs), 919(s), 892(s),
794(s), 754(d), 568(s), 532(s).
2
CH217), 1.60 (d, JHH = 12.88 Hz, 1H, CH217’), 4.51 (m, 1H,
CH18), 1.26 (m, 3H, CH319), 1.29 (m, 3H, CH320), 3.88 (m,
1H, CH21), 1.20 (m, 6H, CH322, CH323), 5.70 (d, 3JHH = 15.7 Hz,
3
2H, CH24), 6.52 (m, 1H, CH25), 1.64 (d, JHH = 6.98 Hz, 3H,
CH326), 3.37 (m, 1H, CH27), 1.35 (m, 3H, CH328), 1.37(m,
3H, CH329), 3.66 (m, 1H, CH30), 1.11 (m, 3H, CH331),
1H NMR (500 MHz, [D8]THF, 297 K): d = 6.95 (d, JHH = 7.12 Hz,
3
3
1H, CH3), 6.86 (m, 1H, CH4), 6.98(d, JHH = 6.87 Hz 1H, CH5),
1.16(m, 3H, CH332) ppm (Fig. 4).13
C NMR (125 MHz,
2
2
4.37(d, JHH = 26.34 Hz, 1H, CH27), 4.55 (d, JHH = 26.34 Hz, 1H,
[D8]THF, 297 K): d = 158.17(C1), 148.02(C2), 123.43(C3),
123.02(C4), 123.53(C5), 146.54(C6), 69.56(C7), 184.13(C8),
2
CH27’), 7.20 (m, 3H,CH11–CH13), 1.44 (d, JHH = 4.96 Hz, 1H,
2
CH215), 1.59 (d, JHH = 12.90 Hz, 1H, CH215’), 5.34(m, 1H, CH16),
147.17(C9),
124.43(C13),
139.71(C10),
140.20(C14),
124.17(C11),
50.72(C15),
127.13(C12),
106.71(C16),
2
2
1.43 (d, JHH = 7.96 Hz, 1H, CH217), 1.62 (d, JHH = 12.94 Hz, 1H,
CH217’), 4.50 (m, 1H, CH18), 1.38 (m, 3H, CH319), 1.40 (m, 3H,
CH320), 3.86 (m, 1H, CH21), 1.31 (m, 6H, CH322, CH323), 2.88 (m,
2H, CH24), 5.73 (m, 1H, CH25), 5.01 (m, 2H, CH26), 3.32 (m, 1H,
CH27), 1.29 (m, 6H, CH328, CH329), 3.61 (m, 1H, CH30), 1.22 (m,
6H, CH331, CH332) ppm (Fig. 3).
53.97(C17), 28.45(C18), 26.10(C19), 26.26(C20), 28.28(C21),
24.89(C22), 25.15(C23), 124.10(C24), 140.89(C25),
19.27(C26), 29.22(C27), 23.78(C28), 24.00(C29), 29.42(C30),
24.28(C31), 24.62(C32) ppm (Fig. 4).1H NMR (500 MHz,
C6D6, 297 K): d = 7.27 (m, 1H, CH3), 7.23 (m, 1H, CH4),
7.32(m, 1H, CH5), 4.68(d, 2JHH = 25.30 Hz, 1H, CH27), 4.90 (d,
2JHH = 25.30 Hz, 1H, CH27’), 7.06 (m, 3H,CH11–CH13), 1.79
13C NMR (125 MHz, [D8]THF, 297 K): d = 157.84(C1),
147.87(C2), 123.43(C3), 123.06(C4), 123.54(C5), 146.33(C6),
72.82(C7), 191.36(C8), 146.67(C9), 139.26(C10), 124.41(C11),
127.33(C12), 124.67(C13), 139.61(C14), 50.62(C15), 106.39(C16),
2
2
(d, JHH = 12.98 Hz, 1H, CH215), 2.00 (d, JHH = 4.27 Hz, 1H,
26
26
23
6
29
23
6
29
25
25
28
28
27
9
22
7
27
9
21
22
7
21
24
8
24
10
5
11
13
8
10
5
11
13
12
N
N
4
N
N
12
1
1
Ni
Ni
17
15
17
15
3
14
3
14
2
2
16
16
30
30
18
18
19
19
32
32
31
31
20
20
Fig. 3. Numbering scheme of carbon atoms in 3.
Fig. 4. Numbering scheme of carbon atoms in 4.