Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201800151
ARTICLE
resulting green solid was recrystallized by slow diffusion of diethyl ether
into a concentrated solution of the compound in dichloromethane.
4.74 (s, 5H, CpH), 2.36 (s, 3H, p’’-CH
13C{1H} NMR (100.6 MHz, CDCl ): 160.9 (d, 2JPC = 24.9 Hz, C1), 142.2
d, 2
3 3
), 1.93, 1.64 (2×br, 2×3H, 2×o’’-CH ).
3
(
JPC = 12.6 Hz, C9), 140.2 (s, Ci’’), 136.2 (s, C7), 135.2 (br, Ci), n.b.
(Ci’), 132.6 (d, 2JPC = 11.6 Hz, Co), 133.3 (s, Co’’), 132.6 (d, 2
5-Cyclopentadienido)[1-(2-(diphenylphosphino)benzyl)-3-methyl-
J
PC = 22.0
(
3
Hz, C5), 131.4 (br, Co’, Cp, Cp’, C8), 131.3 (d, JPC = 8.0 Hz, Cm’’), 132.6
2
(
H-imidazol-2-ylidene]nickel(II) hexafluorophosphate (2a): 208 mg
0.53 mmol) of 1a, 100 mg (0.53 mmol) of nickelocene, 30 mL of tetra-
hydrofuran, 10 mL of dichloromethane and 195 mg (1.06 mmol) of KPF
green solid (88%). Elemental analysis calcd. for C28 NiP (625.18):
(
4
s, Cp’’),129.5 (d, 3JPC = 7.2 Hz, Cm), 129.5 (br, Cm’, C6), 128.1 (d, JPC
=
3
3.5 Hz, C10), 126.2, 124.8 (2×s, C2, C3), 94.5 (CpC), 54.1 (d, JPC = 10.7
6
,
3 3 3
), 17.9 (o’’-CH ):
). 31P{1H} NMR (162.0 MHz, CDCl
Hz, C4), 21.2 (p’’-CH
23.33 (s), -144.17 (hept, 1JPF = 712.8 Hz). 19F{1H} NMR (376.5 MHz,
H
26
F
6
N
2
2
1
C 53.79, H 4.19, N 4.48, found: C 53.80, H 4.34, N 4.51%. H NMR (400.1
MHz, CDCl
1
-1
): 8.19 (dd, 3JHH = 3JPH = 5.9 Hz, 1H, H9), 8.05 (d, 3JHH = 1.8
3
CDCl ): -72.90 (hept, JPF = 712.7 Hz). IR (ATR, cm ): 3148w, 2968w,
3
3
1612w, 1569w, 1480m, 1437m, 1410m, 1281m, 1238m, 1114w, 1089m,
1021w, 935w, 877m, 829s, 792s, 747s, 692s.
Hz, 1H, H2/3), 7.56 (t, JHH = 7.6 Hz, 1H, H8), 7.46-7.27 (m, 8H, H7, Ho,
Ho’, Hm’, Hp’), 7.23 (t, JHH = 7.6 Hz, 1H, Hp), 7.09 (ddd, 3JHH = 8.3 Hz,
3
4JPH = 11.4 Hz, 4
J
PH = 1.7 Hz, 2H, Hm), 6.82 (ddd, 3JHH = 7.9 Hz, 4
J
=
PH
2.1 Hz, 4
J
2
HH = 1.4 Hz, 1H, H6), 6.79 (d, JHH = 1.8 Hz, 1H, H2/3), 6.74,
3
(Cyanido)( -cyclopentadienido)[1-(2-(diphenylphosphino)benzyl)-3-
5
1
6
.09 (2×d, JHH = 14.7 Hz, 2×1H, H4, H4‘), 5.39 (s, 5H, CpH), 3.14 (s, 3H,
methyl-2H-imidazol-2-ylidene]nickel(II) (3): 467 mg (0.91 mmol) of the
nickel(II) complex 2a (used without further purification) and 272 mg (0.96
mmol) of tetra(n-butyl)ammonium cyanide were dissolved in 40 mL of
dichloromethane. The mixture was heated to reflux for 16 h. After removing
the solvent, the product was purified by column chromatography (silica,
dichloromethane with 5% of methanol). It was recrystallized by slow dif-
fusion of diethyl ether into a dichloromethane solution. Red crystals (79%).
2
CH
3
). 13C{1H} NMR (100.6 MHz, CDCl
3
): 157.3 (d, JPC = 38.6 Hz, C1),
2
1
1
1
4
1
1
1
41.9 (d, JPC = 12.0 Hz, C9), 136.2 (s, C7), 135.3 (d, JPC = 46.7 Hz, Ci),
32.5 (d, JPC = 8.9 Hz, C5), 132.9 (d, JPC = 2.4 Hz, Cp), 132.2 (d, 1JPC
2
4
=
3.2 Hz, Ci‘), 132.2 (d, JPC = 11.4 Hz, Co), 131.6 (d, 2JPC = 11.4 Hz, Co’),
31.4 (s, C8), 131.1 (d, JPC = 2.6 Hz, Cp’),129.2 (d, 3JPC = 10.6 Hz, Cm),
28.9 (d, 3JPC = 10.7 Hz, Cm’), 128.9 (s, C6), 125.7, 125.4 (2×s, C2, C3),
25.5 (d, JPC = 47.7 Hz, C10), 93.0 (s, CpC), 53.5 (d, 3JPC = 5.4 Hz, C4),
2
4
Elemental analysis calcd. for C29
26 3 2 2
H N NiP∙CH Cl (591.16): C 60.95, H
3
J
7.6 (CH
3
). 31P{1H} NMR (162.0 MHz, CDCl
3
): 25.86 (s), -144.25 (hept,
4.77, N 7.11, found: C 60.74, H 4.94, N 7.02%. 1H NMR (400.1 MHz,
1
PF = 713.0 Hz). 19F{1H} NMR (376.5 MHz, CDCl
1
3
): -73.06 (d,
J
PF
=
CDCl
3
): 7.42-7.37 (m, 6H, Ho, Hp), 7.35-7.28 (m, 5H, Hm, H9), 7.22 (td,
-
1
3JHH = 7.9 Hz,
4
712.5 Hz). IR (ATR, cm ): 3143w, 2353w, 1568w, 1482m, 1461m, 1436m,
1404m, 1356m, 1289w, 1233m, 1182m, 1098m, 1054w, 923w, 878m,
825s, 747s, 724s, 711m, 695s, 685s.
J
HH = 1.3 Hz, 1H, H8), 6.99-6.94 (m, 2H, H6, H7), 6.88,
6.77 (2×d, 3JHH = 2.0 Hz, 2H, H3), 5.77 (br, 2H, H4), 5.14 (s, 5H, CpH),
4.01 (s, 3H, CH ): 167.1 (C1),
) ppm. 13C{1H} NMR (100.6 MHz, CDCl
40.0 (d, 1JPC = 23.1 Hz, Ci), 135.8 (d, JPC = 15.3 Hz, C10), 135.3 (d, 2JPC
3
3
1
2
5-Cyclopentadienido)[1-(2-(diphenylphosphino)benzyl)-3-tert-bu-
= 9.0 Hz, C5), 134.2 (d, J
PC = 19.9 Hz, Co), 133.5 (s, C7), 129.6, 128.3
(
(
2×s, C6, C8), 129.4 (s, Cp), 128.9 (d, 3JPC = 7.2 Hz, Cm), 128.1 (d, 2JPC
tyl-2H-imidazol-2-ylidene]nickel(II) hexafluorophosphate (2b): 200 mg
0.46 mmol) of 1b, 87 mg (0.46 mmol) of nickelocene, 25 mL of
tetrahydrofuran, 10 mL of dichloromethane and 169 mg (0.92 mmol) of
KPF , green solid (67%). Elemental analysis calcd. for C31 NiP
667.26): C 55.80, H 4.83, N 4.20, found: C 55.71, H 4.97, N 4.23%. 1H
=
4.6 Hz, C9), 125.6 (s, CN), 124.0, 122.5 (2s, C2, C3), 90.9 (s, CpC), 53.1
). 31P{1H} NMR (162.0 MHz, CDCl
): -
6.04. IR (ATR, cm ): 3163w, 3131w, 3104w, 3054w, 3012w, 2938w,
(
(d, JPC = 28.0 Hz, C4), 38.9 (s, CH
3
3
-
1
1
6
H F N
32 6 2
2
2109s, 1587w, 1568w, 1455m, 1432s, 1352m, 1310w, 1236s, 1198m,
1090m, 1068m, 996m, 979m, 837w, 795s, 752s, 744s, 728s, 796s, 669m.
(
2
NMR (400.1 MHz, CD
Hz, 1H, H4), 7.57 (tt, JHH = 7.6 Hz,
2
Cl
2
): 7.69-7.66 (m, 1H, H9), 7.68 (d, JHH = 14.9
3
4
4
J
PH = JHH = 1.3 Hz, 1H, H8), 7.54-
.42 (m, 8H, H7, Ho, Ho’, Hm’, Hp’), 7.35 (d, JHH = 2.1 Hz, 1H, H2/3), 7.29
3
7
(
Synthesis of the nickel(II) complexes 4a and 4d: One equivalent of the
sulfidated imidazolium salt and one equivalent of nickelocene were
dissolved in tetrahydrofuran and heated to reflux for 18 h under an
atmosphere of nitrogen. After cooling to room temperature, the red
suspension was filtered. The solvent was removed from the filtrate under
vacuum, the solids were washed with diethyl ether.
t, 3JHH = 7.7 Hz, 1H, Hp), 7.15 (ddd, JHH = 7.0 Hz, 4JPH = 11.5 Hz, JPH
3
4
=
3
1
.6 Hz, 2H, Hm), 7.04, (d, JHH = 2.1 Hz, 1H, H2/3), 6.95 (ddd, 3JHH = 7.9
Hz, JPH = 10.9 Hz, 4JHH = 1.1 Hz, 1H, H6), 5.37 (s, 5H, CpH), 5.16 (d, JHH
4
2
=
14.9 Hz, 1H, H4’), 1.20 (s, 9H, H12). 13C{1H} NMR (100.6 MHz, CD
2
Cl
2
):
152.0 (d, 2
J
PC = 33.0 Hz, C1), 142.1 (d, 2
J
PC = 12.8 Hz, C9), 137.6 (s,
C7), 136.2 (d, JPC = 46.7 Hz, Ci), 133.1 (d, 4JPC = 2.3 Hz, Cp), 133.0 (d,
2JPC = 10.6 Hz, Co), 131.8 (d, 2JPC = 11.0 Hz, Co’), 131.2 (d, 2JPC = 9.1 Hz,
C5), 131.2 (s, C8), 130.9 (d, 1JPC = 46.2 Hz, Ci’), 131.6 (d, 4JPC = 2.6 Hz,
Cp’),129.9 (s, C6), 129.8 (d, 3JPC = 10.4 Hz, Cm), 129.6 (d, 3JPC = 10.6 Hz,
Cm’), 127.3 (d, JPC = 46.7 Hz, C10), 124.3, 123.3 (2×s, C2, C3), 95.9 (s,
1
5
Chlorido( -cyclopentadienido)[1-(2-(diphenylphosphino)benzyl)-3-
methyl-2H-imidazol-2-ylidene]nickel(II) (4a): 202 mg (0.48 mmol) of
1aS, 91.0 mg (0.48 mmol) of nickelocene, 40 mL of tetrahydrofuran. Re-
crystallization by slow diffusion of diethyl ether into a dichloromethane
solution, red crystals (97%). Elemental analysis calcd. for
CpC), 59.2 (s, C11), 55.6 (d, JPC = 7.2 Hz, C4), 31.2 (C12). 31P{1H} NMR
3
1
(162.0 MHz, CD
2
Cl
2
): 19.12 (s), -144.43 (hept, JPF = 710.6 Hz). 19F{1H}
C
28
H
26ClN
2
NiPS∙(CH
2
Cl
2
)
0.1 (556.22): C 60.68, H 4.75, N 5.04, S 5.76,
): δ
.86 (br, 4H, Ho), 7.55 (br, 4H, Hm), 7.42 (br, 3H, Hp, H9), 7.29-7.07 (m,
H, H8), 7.01-6.75 (m, 4H, H2, H3, H6, H7), 5.22 (br, 2H, H4), 4.95 (br,
H, CpH), 4.30 (s, 3H, CH ) broad resonances probably due to paramag-
1
NMR (376.5 MHz, CD
2
Cl
2
): -73.17 (d, JFP = 710.7 Hz). IR (ATR, cm-1):
found: C 60.56, H 4.94, N 5.07, S 5.89. 1H NMR (400.1 MHz, CDCl
3
2983w, 1923w, 1549m, 1479m, 1447m, 1435m, 1379m, 1310m, 1237m,
7
1
5
1191m, 1118m, 1094m, 876m, 828s, 744s, 694s, 655m.
3
(
2
(
5-Cyclopentadienido)[1-(2-(diphenylphosphino)benzyl)-3-mesityl-
H-imidazol-2-ylidene]nickel(II) hexafluorophosphate (2c): 200 mg
0.40 mmol) of 1c, 76 mg (0.40 mmol) of nickelocene, 25 mL of
tetrahydrofuran, 10 mL of dichloromethane and 148 mg (0.80 mmol) of
KPF green solid (92%). Elemental analysis calcd. for
netic impurities. 13C{1H} NMR (100.6 MHz, CDCl
3
): δ 161.3 (C1), 140.5 (d,
2JPC = 8.1 Hz, C9), 133.0-122.0 div. overlapping signals, 131.5 (d, JPC
3
=
9.1 Hz, C8), 129.1 (d, 3JPC = 12.3 Hz, Cm), 127.6 (d, JPC =12.3 Hz, C6),
3
124.1, 122.6 (2×s, C2, C3), 91.7 (CpC), 52.7 (d, 3JPC = 6.3 Hz, C4), 38.9
(CH
3 3
). 31P{1H} NMR (162.0 MHz, CDCl ): δ 41.69 (s). IR (KBr, cm-1):
6
,
C
36
H
33
F
6
NiN
2
P
2
∙CH
2
Cl
2
(813.25): C 54.65, H 4.34, N 3.44, found: C 54.41,
): 7.75-7.68 (m, 1H, H9),
3157w, 3124m, 3101w, 3045w, 2918w, 1624w, 1589m, 1569m, 1478m,
1470m, 1435s, 1409s, 1343m, 1310m, 1237s, 1211m, 1096s, 1070m,
997m, 834m, 790s, 753s, 737s, 723s, 712s, 695s, 638s, 614m, 522s,
1
H 4.44, N 3.54%. H NMR (400.1 MHz, CDCl
3
7
.72 (d, 3JHH = 1.8 Hz, 1H, H2/3), 7.67-7.33(m, 11H, H7, H8, Ho, Ho’, Hm’,
Hm’’, Hm’’, Hp’), 7.29 (t, JHH = 7.9 Hz, 1H, Hp), 7.21 (ddd, 3JHH = 8.3 Hz,
3
496m, 450m. ESI-MS (m/z): [M-Cl]+ calcd: 511.09, found: 511.13, [M-
4JPH = 11.4 Hz, 4
J
PH = 1.7 Hz, 1H, Hm), 7.00 (br, 2H, H6, Hm’), 6.79 (d,
C H
5 4
NiCl] calcd: 389.12, found: 389.14.
+
3JHH = 1.9 Hz, 1H, H2/3), 6.33, 5.24 (2×dbr, JHH = 10.5 Hz, 2×1H, H4, H4’),
2
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