Organometallics
Article
CtrzCH2CH2CH2), 1.10−1.01 (m, 6H, NCH2CH2CH2CH3 and
CtrzCH2CH2CH2CH3). The complex appeared to be unstable in
solution, and longer measurements were not possible. The 13C NMR
data were therefore extracted from two-dimensional HSQC and
HMBC experiments: 13C{1H} NMR (126 MHz, CD2Cl2): δ 138.2
(Ctrz−Ni), 148.0 (Ctrz−Bu), 91.0 (C5H5), 54.5 (NCH2), 35.7
(NCH3), 25.5 (CtrzCH2), 32.1 (NCH2CH2), 31.2 (CtrzCH2CH2),
22.6 (NCH2 CH2 CH2 ), 19.8 (Ct r z CH2 CH2 CH2 ), 13.5
(NCH2CH2CH2CH3 and CtrzCH2CH2CH2CH3). Recrystallization
and hence also microanalyses failed due to the instability. HR-MS:
m/z calculated for C16H26N3Ni+[M − Cl]+, 318.1480; found,
318.1477.
Complex 4a(BF4). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol), triazolium salt
2a(BF4) (433 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in 16 h
(yield 112 mg, 35%). 1H NMR (400 MHz, CD3OD): δ 7.65−7.60 (m,
6H, HPh), 7.42−7.38 (m, 4H, HPh), 5.28 (s, 5H, C5H5), 3.82 (t, JHH
=
7.4 Hz, 4H, NCH2), 3.79 (s, 6H, NCH3), 1.66 (quintet, JHH = 7.4 Hz,
4H, NCH2CH2), 1.32 (sextet, JHH = 7.4 Hz, 4H, CH2CH3), 0.97 (t,
JHH = 7.4 Hz, 6H, CH2CH3). 13C{1H} NMR (101 MHz, CD2Cl2): δ
150.08 (Ctrz−Ni), 148.46 (Ctrz−Ph), 131.89, 131.27, 130.22, 129.93 (4
× CPh), 92.24 (C5H5), 54.82 (NCH2), 37.42 (NCH3), 32.87
(NCH2CH2), 20.95 (CH2CH3), 13.97 (CH2CH3). Anal. Calcd for
C31H39BF4N6Ni (641.18): C, 58.07; H, 6.13; N, 13.11. Found: C,
57.79; H, 6.02; N, 13.19. HR-MS: m/z calculated for C31H39N6Ni+ [M
− BF4]+, 553.2590; found, 553.2568.
Complex 3c-I. This compound was prepared according to the
general method from nickelocene (188 mg, 1.0 mmol) and triazolium
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Complex 4b(I). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol), triazolium salt
2b(I) (323 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in 16 h
salt 2c(I) (363 mg, 1.0 mmol) in 4 h (yield 179 mg, 37%). H NMR
(400 MHz, CDCl3): δ 8.63 (d, JHH = 7.7 Hz, 2H, HPh−N ortho), 8.08 (d,
JHH = 7.7 Hz, 2H, HPh−C ortho), 7.69−7.56 (m, 6H, HPh−N and HPh−C),
4.82 (s, 5H, C5H5), 4.03 (s, 3H, NCH3). 13C{1H} NMR (126 MHz,
CDCl3): δ 148.76 (Ctrz−Ph) 148.65 (Ctrz−Ni), 130.89, 130.20, 130.11,
130.02, 128.95, 128.87, 128.84, 125.63 (8 × CPh), 92.02 (C5H5), 37.43
(NCH3). Anal. Calcd for C20H18IN3Ni (485.97): C, 49.43; H, 3.73; N,
8.65. Found: C, 49.28; H, 3.58; N, 8.42.
Complex 3c-Cl. This compound was prepared according to the
general method from nickelocene (188 mg, 1.0 mmol) and triazolium
salt 2c(Cl) (271 mg, 1.0 mmol) in 4 h (yield 316 mg, 80%). 1H NMR
(400 MHz, CDCl3): δ 8.79 (d, JHH = 7.5 Hz, 2H, HPh−N ortho), 8.25 (d,
JHH = 7.5 Hz, 2H, HPh−C ortho), 7.73−7.60 (m, 6H, HPh−N and HPh−C),
4.64 (s, 5H, C5H5), 4.09 (s, 3H, NCH3). 13C{1H} NMR (101 MHz,
CDCl3): δ 148.41(Ctrz−Ph), 148.23 (Ctrz−Ni), 130.89, 130.14, 130.09,
129.16, 129.06, 128.99, 128.82, 125.42 (8 × CPh), 91.75 (C5H5), 37.61
(NCH3). Anal. Calcd for C20H18ClN3Ni (394.52): C, 60.89; H, 4.60;
N, 10.65. Found: C, 60.89; H, 4.55; N, 10.44.
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(yield 61 mg, 19%). H NMR (400 MHz, CDCl3): δ 5.26 (s, 5H,
C5H5), 4.52 (t, JHH = 7.6 Hz, 4H, NCH2), 4.06 (s, 6H, NCH3), 2.97 (t,
JHH = 7.4 Hz, 4H, CtrzCH2), 1.92 (quintet, JHH = 7.6 Hz, 4H,
NCH2CH2), 1.64−1.50 (m, 8H, CtrzCH2CH2 and NCH2CH2CH2),
1.47−1.41 (m, 4H, CtrzCH2CH2CH2), 1.04 (t, JHH = 7.6 Hz, 6H,
NCH2CH2CH2CH3), 1.01 (t, JHH
= 7.4 Hz, 6H, CH3,
CtrzCH2CH2CH2CH3). 13C{1H} NMR (101 MHz, CDCl3): δ
148.17 (Ctrz−Bu), 145.41 (Ctrz−Ni), 90.60 (C5H5), 54.71 (NCH2),
37.90 (NCH3), 32.15 (NCH2CH2), 31.07 (CtrzCH2CH2), 26.37
(CtrzCH2), 23.11 (CtrzCH2CH2CH2), 20.21 (NCH2CH2CH2), 14.14
(CtrzCH2CH2CH2CH3), 13.93 (NCH2CH2CH2CH3). Anal. Calcd for
C27H47IN6Ni (641.30): C, 50.57; H, 7.39; N, 13.10. Found: C, 50.89;
H, 7.62; N, 12.38. HR-MS: m/z calculated for C27H47N6Ni+ [M − I]+,
513.3216; found, 513.3221.
Complex 4b(Cl). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol) and triazolium
salt 2b(Cl) (232 mg, 1.0 mmol) in 16 h (yield 49 mg, 18%). 1H NMR
(400 MHz, CDCl3): δ 5.25 (s, 5H, C5H5), 4.50 (t, JHH = 7.7 Hz, 4H,
NCH2), 4.09 (s, 6H, NCH3), 2.97 (t, JHH = 7.6 Hz, 4H, CtrzCH2), 1.92
(quintet, JHH = 7.7 Hz, 4H, NCH2CH2), 1.66−1.50 (m, 8H,
CtrzCH2CH2 and NCH2CH2CH2), 1.45 (sextet, JHH = 7.6 Hz, 4H,
CtrzCH2CH2CH2), 1.09−1.01 (m, 12H, NCH2CH2CH3 and
CtrzCH2CH2CH3). 13C{1H} NMR (101 MHz, CDCl3): δ 148.07
(Ctrz−Bu), 146.16 (Ctrz−Ni), 90.66 (C5H5), 54.61 (NCH2), 37.39
(NCH3), 32.16 (NCH2CH2), 31.44 (CtrzCH2CH2), 26.00 (CtrzCH2),
23.10 (CtrzCH2CH2CH2), 20.21 (NCH2CH2CH2), 14.13
(CtrzCH2CH2CH2CH3), 13.92 (NCH2CH2CH2CH3). Anal. Calcd for
C27H47N6NiCl (548.29)·1.5H2O: C, 56.22; H, 8.74; N, 14.57. Found:
C, 56.49; H, 8.55; N, 14.51.
Complexes 4b(OTf). This compound was prepared according to
the general method from nickelocene (97 mg, 0.51 mmol), triazolium
salt 2b(OTf) (345 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in
16 h (yield 72 mg, 22%). 1H NMR (400 MHz, CDCl3): δ 5.25 (s, 5H,
C5H5), 4.50 (t, JHH = 7.6 Hz, 4H, NCH2), 3.97 (s, 6H, NCH3), 2.90 (t,
JHH = 7.4 Hz, 4H, CtrzCH2), 1.92 (quintet, JHH = 7.6 Hz, 4H,
NCH2CH2), 1.61−1.49 (m, 8H, CtrzCH2CH2 and NCH2CH2CH2),
1.45 (sextet, JHH = 7.4 Hz, 6H, CtrzCH2CH2CH2), 1.08−1.01 (m, 12H,
NCH2CH2CH2CH3 and CtrzCH2CH2CH2CH3). 13C NMR (101 MHz,
CDCl3): δ 148.13 (Ctrz−Bu), 145.01 (Ctrz−Ni), 90.58 (C5H5), 54.50
(NCH2), 36.86 (NCH3), 32.13 (NCH2CH2), 31.39 (CtrzCH2CH2),
25.78 (CtrzCH2), 23.08 (CtrzCH2CH2CH2), 20.19 (NCH2CH2CH2),
14.08 (CtrzCH2CH2CH2CH3), 13.91 (NCH2CH2CH2CH3). Anal.
Calcd for C28H47F3N6NiO3S (662.27): C, 50.69; H, 7.14; N, 12.67.
Found: C, 50.62; H, 7.00; N, 12.39.
Complex 4a(I). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol), triazolium salt
2a(I) (343 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in 16 h
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(yield 95 mg, 28%). H NMR (400 MHz, CD2Cl2): δ 7.61−7.59 (m,
10 H, HPh), 5.27 (s, 5H, C5H5), 3.87 (s, 6H, NCH3), 3.65 (t, JHH = 7.6
Hz, 4H, NCH2), 1.63−1.54 (m, 4H, NCH2CH2), 1.33−1.18 (m, 4H,
CH2CH3), 0.93 (t, JHH = 7.4 Hz, 6H, CH2CH3). 13C{1H} NMR (101
MHz, CD2Cl2): δ 148.40 (Ctrz−Ni), 147.44 (Ctrz−Ph), 131.69, 130.66,
129.55, 128.81 (4 × CPh), 91.51 (C5H5), 54.54 (NCH2), 38.33
(NCH3), 32.46 (NCH2CH2), 20.50 (CH2CH3), 13.94 (CH2CH3).
Anal. Calcd for C31H39IN6Ni (681.28): C, 54.65; H, 5.77; N, 12.34.
Found: C, 54.80; H, 5.64; N, 12.00.
Complex 4a(Cl). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol) and triazolium
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salt 2a(Cl) (251 mg, 1.0 mmol) in 16 h (yield 118 mg, 40%). H
NMR (400 MHz, CDCl3): δ 7.83−7.77 (m, 10H, HPh), 5.28 (s,
5H,C5H5), 4.00 (s, 6H, NCH3), 3.52 (t, JHH = 7.4 Hz, 4H, NCH2),
1.54 (quintet, JHH = 7.4 Hz, 4H, NCH2CH2), 1.26 (sextet, JHH = 7.4
Hz, 4H, CH2CH3), 0.93 (t, JHH = 7.4 Hz, 6H, CH2CH3). 13C{1H}
NMR (101 MHz, CD2Cl2): δ 148.43 (Ctrz−Ni), 147.47 (Ctrz−Ph),
131.71, 130.59, 129.53, 128.80 (4 × CPh), 91.55 (C5H5), 54.52
(NCH2), 38.31 (NCH3), 32.42 (NCH2CH2), 20.45 (CH2CH3), 13.90
(CH2CH3). Anal. Calcd for C31H39IN6Ni (589.83): C, 63.13; H, 6.66;
N, 14.25. Found: C, 62.60; H, 6.47; N, 14.03.
Complex 4a(OTf). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol), triazolium salt
2a(OTf) (365 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in 16
1
h (yield 229 mg, 65%). H NMR (400 MHz, CD2Cl2): δ 7.71−7.54
(m, 6H, HPh), 7.46−7.34 (m, 4H, HPh), 5.26 (s, 5H, C5H5), 3.79 (s,
Complex 4b(BF4). This compound was prepared according to the
general method from nickelocene (97 mg, 0.51 mmol), triazolium salt
2b(BF4) (310 mg, 1.0 mmol), and NEt4Cl (166 mg, 1.0 mmol) in 16
6H, NCH3), 3.68 (t, JHH = 7.4 Hz, 4H, NCH2), 1.60 (quintet, JHH
=
7.4 Hz, 4H, NCH2CH2), 1.26 (sextet, JHH = 7.4 Hz, 4H, CH2CH3),
0.94 (t, JHH = 7.4 Hz, 6H, CH2CH3). 13C{1H} NMR (101 MHz,
CD2Cl2): δ 148.52 (Ctrz−Ni), 148.49 (Ctrz−Ph), 131.22, 130.76,
129.67, 128.81 (4 × CPh), 91.57 (C5H5), 54.54 (NCH2), 37.64
(NCH3), 32.41 (NCH2CH2), 20.49 (CH2CH3), 13.94 (CH2CH3).
Anal. Calcd for C32H39F3N6NiO3S (703.44): C, 54.64; H, 5.59; N,
11.95. Found: C, 54.46; H, 5.38; N, 11.75.
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h (yield 6 mg, 4%). H NMR (400 MHz, CD3OD): δ 5.34 (s, 5H,
C5H5), 4.51 (t, JHH = 7.6 Hz, 4H, NCH2), 4.00 (s, 6H, NCH3), 2.99 (t,
JHH = 7.4 Hz, 4H, CtrzCH2), 1.96−1.84 (m, 4H, NCH2CH2), 1.63−
1.52 (m, 8H, CtrzCH2CH2 and NCH2CH2CH2), 1.40 (sextet, JHH = 7.4
Hz, 4H, CtrzCH2CH2CH2), 1.08 (t, JHH = 7.6 Hz, 6H,
NCH2 CH2 CH2 CH3 ), 1. 01 (t, JH H
= 7.4 Hz, 6H,
H
dx.doi.org/10.1021/om500593s | Organometallics XXXX, XXX, XXX−XXX