Carbene–Nickel(0) Complexes
FULL PAPER
3
5.29 (sept, 8H, JH,H = 6.9 Hz, iPr-CH), 6.75 ppm (s, 8H, NCHCHN);
Compound 5: Complex 1 (363 mg, 0.42 mmol) was dissolved in toluene
(20 mL) and hexafluorobenzene (0.12 mL, 1.00 mmol) was added. The re-
sulting yellow solution was stirred overnight. The reaction mixture was
then filtered through a pad of Celite and all volatile material was re-
moved from the filtrate in vacuo. The remaining yellow solid was sus-
pended in 20 mL of hexane, filtered, and dried in vacuo to afford 5 as a
13C{1H} NMR (100 MHz, C6D6, 258C): d=23.81 (iPr-CH3), 23.98 (iPr-
CH3), 31.96 (COD-CH2), 33.52 (COD-CH2), 38.57 (COD-CH), 50.58
(iPr-CH), 50.69 (iPr-CH), 54.57 (COD-CH), 113.93 (NCCN), 114.29
(NCCN), 204.19 (NCN), 205.28 ppm (NCN); IR (KBr): n˜ =3216 (w),
2964 (s), 2925 (s), 2814 (m), 1659 (w), 1599 (w), 1466 (m), 1410 (s), 1393
(s), 1366 (m), 1279 (m), 1259 (s), 1217 (vs), 1130 (m), 1085 (w), 1006 (m),
982 (m), 925 (w), 875 (w), 793 (m), 673 (s), 549 cmꢀ1 (m); elemental anal-
ysis calcd (%) for C44H76N8Ni2 (834.5): C 63.33, H 9.18, N 13.34; found:
C 63.56, H 9.09, N 12.99; MS: m/z (%): 362.2 (24) [(iPr2Im)2Ni]+, 320.1
(8) [(iPr2Im)2NiꢀPr]+.
Compound 2: Ethylene was passed through a solution of complex 1
(363 mg, 0.42 mmol) in toluene (30 mL) at room temperature. All volatile
material was removed in vacuo, and the residue was suspended in 20 mL
of hexane, filtered, and dried in vacuo to afford 2 as a yellow powder
(280 mg, 72%). Crystals suitable for X-ray diffraction were obtained
from saturated hexane solutions of 2 at 08C 1H NMR (400 MHz, C6D6,
1
yellow powder (360 mg, 65%). H NMR (400 MHz, C6D6, 258C): d=1.08
(brs, 12H, CH3), 1.40 (brs, 12H, CH3), 6.25 (s, 4H, NCHCHN), 6.51 ppm
(sept, 4H, 3JH,H =6.8 Hz, iPr-CH3); 19F NMR (376.4 MHz, C6D6, 258C,
3
CFCl3): d=ꢀ116.0 (d, 2F, 3JF,F =28.7 Hz, aryl-Fo), ꢀ163.3 (t, 1F, JF,F
=
20.3 Hz, aryl-Fp), ꢀ165.0 (m, 2F, aryl-Fm), ꢀ373.7 ppm (s, 1F, Ni-F); IR
(KBr): n˜ =438 (m), 477 (m), 578 (w), 673 (m), 708 (w), 732 (m), 777 (m),
951 (s), 1013 (s), 1130 (m), 1215 (s), 1226 (s), 1263 (m), 1370 (m), 1394
(m), 1441 (s), 1495 (s), 2876 (w), 2936 (m), 2980 (s), 3050 (s), 3118 cmꢀ1
(w); MS: m/z (%): 549.2 (3) [M]+, 362.3 (40) [(iPr2Im)2Ni]+.
Compound 6: Complex 1 (363 mg, 0.42 mmol) and biphenylene (152 mg,
1.00 mmol) were dissolved in toluene (30 mL) and stirred overnight. Un-
dissolved components were removed by filtration through a pad of Celite
and all volatiles were removed from the filtrate in vacuo. The remaining
orange solid was treated with small portions of hexane and dried in
vacuo to afford 6 as an orange powder (345 mg, 66%). Crystals suitable
for X-ray diffraction were obtained from saturated solutions of 6 in di-
3
258C): d=1.13 (d, 24H, JH,H = 6.8 Hz, CH3), 1.95 (s, 4H, CH2), 5.41
(sept, 4H, JH,H
3
= 6.8 Hz, iPr-CH), 6.48 ppm (s, 4H, NCHCHN);
13C{1H} NMR (100 MHz, C6D6, 258C): d=22.24 (iPr-CH3), 24.85 (Cethene),
49.71 (iPr-CH), 113.46 (NCCN), 203.00 ppm (NCN); IR (KBr): n˜ =381
(m), 478 (m), 572 (w), 675 (m), 709 (m), 801 (s), 921 (m), 958 (m), 1018
(vs), 1093 (s), 1139 (m), 1221 (s), 1263 (s), 1288 (m), 1368 (m), 1397 (m),
1415 (m), 1465 (m), 1669 (m), 2870 (m), 2944 (s), 3119 (w), 3158 cmꢀ1
(w); MS: m/z (%): 362.3 (28) [(iPr2Im)2Ni]+.
1
ethyl ether at ꢀ408C. H NMR (400 MHz, C6D6, 258C): d=0.70 (d, 12H,
3JH,H =6.8 Hz, CH3), 1.14 (d, 12H, 3JH,H =6.8 Hz, CH3), 5.43 (sept, 4H,
3JH,H =6.8 Hz, iPr-CH), 6.37 (d, 2H, aryl-Hm), 6.39 (s, 4H, NCHCHN),
6.97 (m, 2H, aryl-Hp), 7.18 (m, 2H, aryl-Hm), 7.70 ppm (m, 2H, aryl-Ho);
13C{1H} NMR (100 MHz, C6D6, 258C): d=23.26 (iPr-CH3), 23.86 (iPr-
CH3), 52.07 (iPr-CH), 116.76 (NCCN), 119.30 (aryl-Cp), 124.52 (aryl-Cm),
125.31 (aryl-Cm), 141.05 (aryl-Co), 161.61 (aryl-Co), 173.51 (aryl-Ci),
193.47 ppm (NCN); IR (KBr): n˜ =575 (w), 669 (m), 676 (m), 692 (m),
708 (m), 735 (s), 878 (w), 991 (m), 1018 (m), 1107 (m), 1131 (m), 1216
(vs), 1258 (w), 1294 (m), 1369 (m), 1390 (s), 1407 (s), 1417 (s), 1467 (m),
1570 (m), 2871 (m), 2929 (s), 2971 (vs), 3034 (s), 3098 (m), 3130 (w),
3159 cmꢀ1 (m); elemental analysis calcd (%) for C30H404N4Ni (515.4):
calcd for C 69.92, H 7.82, N 10.87; found: C 69.34, H 7.95, N 11.21.
Compound 3: Complex 1 (417 mg, 0.50 mmol) and diphenylacetylene
(89.0 mg, 0.50 mmol) were dissolved in toluene (20 mL) and stirred over-
night. Undissolved components were removed by filtration through a pad
of Celite and all volatiles of the filtrate were removed in vacuo to afford
3 as a dark-red powder (310 mg, 57%). Crystals suitable for X-ray dif-
fraction were obtained from saturated solutions of 3 in diethyl ether at
ꢀ408C. 1H NMR (400 MHz, C6D6, 258C): d=1.03 (d, 24H, JH,H
=
3
3
6.8 Hz, CH3), 5.53 (sept, 4H, JH,H
= 6.8 Hz, iPr-CH), 6.55 (s, 4H,
NCHCHN), 7.02 (m, 2H, aryl-Hp), 7.19 (m, 4H, aryl-Hm), 7.61 ppm (d,
4H, JH,H = 7.0 Hz, aryl-Ho); 13C{1H} NMR (100 MHz, C6D6, 258C): d=
3
23.92 (CH3), 51.78 (iPr-CH), 115.78 (NCCN), 124.60 (aryl-Cp), 129.50
(aryl-Cm), 132.60 (aryl-Co), 139.26 (CꢁC), 139.69 (aryl-Ci), 201.49 ppm
(NCN); IR (KBr): n˜ =556 (m), 668 (m), 697 (m), 763 (e), 911 (w), 1006
(w), 1013 (w), 1128 8w), 1214 (vs), 1258 (m), 1274 (m), 1395 (m), 1413
(m), 1472 (m), 1490 (m), 1576 (m), 1741 (m, nCꢁC), 2866 (m), 2932 (m),
2966 (m), 3049 cmꢀ1 (w); elemental analysis calcd (%) for C32H42N4Ni
(541.4): C 70.99, H 7.82, N 10.35; found: C 70.97, H 7.70, N 9.56; MS:
m/z (%): 540 (1) [MꢀH]+, 362.1 (15) [(iPr2Im)2NiꢀH]+.
9,10-Diphenylphenanthrene: Biphenylene (30.4 mg, 0.20 mmol), diphenyl-
acetylene (36.0 mg, 0.20 mmol), and complex 1 (10 mg, 0.012 mmol) were
mixed in an NMR tube and dissolved in C6D6 (1.00 mL). The reaction
mixture was heated to 808C for 30 min. According to 1H NMR spectros-
copy, the yield was greater than 95%. 1H NMR (400 MHz, C6D6, 258C):
d=6.94 (m, 2H, aryl-CH2), 6.98–7.13 (m, 10H, aryl-CHphenyl), 7.41 (m,
2H, aryl-CH3), 7.55 (m, 2H, aryl-CH1), 8.74 ppm (m, 2H, aryl-CH4);
13C{1H} NMR (100 MHz, C6D6, 258C): d=139.17 (aryl-C7), 136.70 (aryl-
C6), 131.55 (aryl-Ci), 130.97 (aryl-C5), 130.37 (aryl-Co), 129.68 (aryl-C1),
126.95 (aryl-Cm), 125.95 (aryl-C2), 125.77 (aryl-C3), 125.70 (aryl-Cp),
121.96 ppm (aryl-C4).
Compound 4: Carbon monoxide was passed through a solution of com-
plex 1 (363 mg, 0.42 mmol) in toluene (30 mL) at room temperature. All
volatile material was removed in vacuo to afford 4 as a yellow powder
(310 mg, 88%). Crystals suitable for X-ray diffraction were obtained
from saturated solutions of 4 in dieth-
yl ether at ꢀ408C. 1H NMR
Table 2. X-ray data collection and processing parameters.
(400 MHz, C6D6, 258C): d=1.05 (d,
2JH,H =6.8 Hz, 24H, CH3), 5.39 (sept,
5JH,H =6.8 Hz, 4H, iPr-CH), 6.49 ppm
(s, 4H, NCHCHN); 13C{1H} NMR
(100 MHz, C6D6, 258C): d=23.63
(iPr-CH3), 51.68 (iPr-CH), 116.19
(NCCN), 198.01 (CO), 205.80 ppm
(NCN); IR (KBr): n˜ =473 (w), 507
(w), 572 (w), 672 (s), 712 (s), 725 (m),
800 (w), 882 (m), 989 (s), 1016 (m),
1079 (m), 1134 (m), 1216 (vs), 1248
(m), 1285 (s), 1367 (s), 1398 (s), 1415
(s), 1466 (m), 1847 (vs, br, nCO), 1927
(vs, br, nCO), 2872 (m), 2931 (m), 2979
(s), 3107 (w), 3142 (w), 3173 cmꢀ1
(w); elemental analysis calcd (%) for
1·C4H8O
2
3
4
6
formula
Fw
C26H46N4NiO
489.38
monoclinic
P21/c
21.7887(14)
–
9.5251(5)
–
4522.0(5)
4
0.867
16183/5652
4147
C20H36N4Ni
391.24
tetragonal
P42/n
17.478(4)
10.101(2)
17.817(4)
108.79(3)
2977.9(10)
8
C32H42N4Ni
541.42
monoclinic
P21/n
9.5275(8)
14.7564(14)
16.6747(12)
–
2342.7(3)
4
C10H16N2ONi
209.61
orthorhombic
Pbcn
20.1563(14)
23.544(2)
27.913(3)
–
13246(2)
8
C120H168N16Ni4
2069.56
orthorhombic
P212121
crystal system
space group
a []16.061(2)
b []9.4571(7)
c []18.5381(18)
b [8]94.962(15)
V [3]2805.2(5)
Z
4
m [mmꢀ1]0.380
total/indep. reflns.
obsd reflns.[a]
parameters
0.677
28737/4409
3227
0.562
18790/7055
4608
0.404
21008/2929
2038
58561/19036
10087
1255
0.0779, 0.1668
297
226
334
123
[c,d]
final R,[b] wR2
0.0560, 0.1334
0.0378, 0.0815
0.0588, 0.1664
0.0350, 0.0811
C20H32N4NiO2 (419.2): calcd for
57.31, 7.69, 13.37; found:
C
C
1
[a]Reflections with I>2s(I). [b] R=ꢀjjFo jꢀjFc jj/ꢀjFo j. [c] wR2 ={ꢀ[w(Fo2ꢀFc2)2]/ꢀ[w(Fo2)2]} = . [d]For data
2
H
N
56.94, H 7.65, N 12.95.
with I>2s(I).
Chem. Eur. J. 2005, 11, 5024 – 5030
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5029