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δ(ppm): −78.65 (s). Anal. Calc. for C29H32F3N3NiO3S: C, 56.33; C28H32N4NiO3: C, 63.30; H, 6.07; N, 10.55. Found: C, 62.99; H,
H, 5.22; N, 6.80. Found: C, 56.31; H, 5.30; N, 6.79%.
6.07; N, 10.64%.
[Ni(η5-C5H5)((CH3)3CCN)(IMes)]+(PF6)− (2g). Obtained from
[Ni(η5-C5H5)(CF3COO)(IMes)] (3a). To
a
solution of
1a (117.0 mg, 0.253 mmol) and KPF6 (62.0 mg, 0.336 mmol, [Ni(η5-C5H5)(IMes)Cl] (1a) (80 mg, 0.173 mmol) in acetonitrile
1.33 eq.) in pivalonitrile (3.0 mL). Yield: 96%, yellow solid (2.0 mL) a solution of CF3CO2Ag (39 mg, 0.173 mmol, 1 eq.) in
1
(159.3 mg, 0.243 mmol). H NMR (400 MHz, CDCl3) δ(ppm): THF (1.0 mL) was added. The colour of the reaction mixture
7.26 (2H, s, HCvCH), 7.13 (4H, bs, m-ArH), 4.75 (5H, s, C5H5), changed immediately from red to yellow. After 1 h of stirring
2.44 (6H, s, p-ArCH3), 2.09 (12H, s, o-ArCH3), 1.24 (9H, s, at room temperature with protection from light the reaction
(CH3)3CCN). 13C{1H} NMR (101 MHz, CDCl3) δ(ppm): 159.9 mixture was filtered through Celite and evaporated in vacuo.
(NCN), 140.2 (ArC), 138.2 (CN), 135.7 (ArC), 134.8 (ArC), 129.8 The resulting red solid was washed with diethyl ether (2 ×
(ArC), 126.1 (HCvCH), 93.9 (C5H5), 30.9 ((CH3)3CCN), 27.6 3 mL) and dried in vacuo to give 63.5 mg of [Ni(C5H5)-
((CH3)3CCN), 21.4 (p-ArCH3), 18.2 (o-ArCH3). 19F NMR (CF3COO)(IMes)] as a red solid (0.117 mmol, 68%). Toluene
(376 MHz, CDCl3) δ(ppm): −73.55 (d, J = 709.0 Hz). 31P NMR could be used instead of acetonitrile, providing 3a in 46%
(162 MHz, CDCl3) δ(ppm): −143.35 (sep, J = 709.0 Hz). ESI MS yield.
m/z (58Ni): 427 ([M − (CH3)3CN − PF6]+). Anal. Calc. for
1H NMR (400 MHz, CDCl3) δ(ppm): 7.11 (6H, s, m-ArH and
C31H38F6N3NiP: C, 56.73; H, 5.84; N, 6.40. Found: C, 56.70; H, HCvCH overlapping), 4.62 (5H, s, C5H5), 2.44 (6H, s, p-ArCH3),
5.77; N, 6.40%.
2.09 (12H, s, o-ArCH3). 13C{1H} NMR (101 MHz, CDCl3)
[Ni(η5-C5H5)(CH3CN)(Bn2-bimy)]+(PF6)−
(2h). Obtained δ(ppm): 166.2 (NCN), 163.8 (q, J = 35.6 Hz, CO), 139.34 (ArC),
from 1e (112.1 mg, 0.245 mmol) and KPF6 (55.0 mg, 136.3 (ArC), 135.6 (ArC), 129.3 (ArC), 124.6 (HCvCH), 114.1 (q,
0.299 mmol, 1.22 eq.) in acetonitrile (2.5 mL). Yield: 41%, J = 291.4 Hz, CF3), 91.3 (C5H5), 21.5 (p-ArCH3), 18.0 (o-ArCH3).
yellow solid (60.8 mg, 0.100 mmol). 1H NMR (400 MHz, CDCl3) 19F NMR (376 MHz, CDCl3) δ(ppm): −74.73 (s). EI MS (70 eV)
δ(ppm): 7.37 (4H, m, ArH), 7.33 (2H, m, ArH), 7.30–7.24 (4H, m/z (58Ni): 540 (M+, 24%), 475 ([M
−
Cp]+, 29), 427
m, ArH), 7.11 (4H, bd, J = 7.1 Hz, ArH), 6.45 (2H, bd, J = ([M
−
CF3CO2]+, 29), 303 (IMes+, 100). Anal. Calc. for
13.5 Hz, CH2), 6.19 (2H, bd, J = 13.8 Hz, CH2), 5.22 (5H, s, C28H29F3N2NiO2: C, 62.14; H, 5.40; N, 5.18. Found: C, 62.18;
C5H5), 2.03 (3H, s, CH3CN). 13C{1H} NMR (101 MHz, CDCl3) H, 5.51; N, 5.20%.
δ(ppm): 174.3 (NCN), 135.7 (ArC), 129.3 (ArC), 129.1 (CH3CN),
[Ni(η5-C5H5)(CF3COO)(SIMes)] (3b). This compound was
128.23 (ArC), 126.2 (ArC), 125.4 (ArC), 124.2 (ArC), 111.5 (ArC), prepared similarly as described for 3a from 1b (90.0 mg,
93.82 (C5H5), 53.1 (CH2Ph), 3.8 (CH3CN). 19F NMR (376 MHz, 0.194 mmol) and CF3CO2Ag (43.0 mg, 0.195 mmol, 1 eq.).
CDCl3) δ(ppm): −73.06 (d, J = 709.2 Hz). 31P NMR (162 MHz, Yield: 63%, red solid (66.3 mg, 0.122 mmol). 1H NMR
CDCl3) δ(ppm): −143.36 (sep, J = 709.2 Hz). ESI MS m/z (400 MHz, CDCl3) δ(ppm): 7.07 (4H, s, m-ArH), 4.62 (5H, s,
(58Ni): 421 ([M
− CH3CN −
PF6]+). Anal. Calc. for C5H5), 3.93 (4H, s, H2C–CH2), 2.40 (6H, s, p-ArCH3), 2.31 (12H,
C28H26F6PN3Ni: C, 55.30; H, 4.31; N, 6.91. Found: C, 55.14; s, o-ArCH3). 13C{1H} NMR (101 MHz, CDCl3) δ(ppm): 199.4
H, 4.41; N, 6.90%.
(NCN), 163.8 (q, J = 35.4 Hz, CO), 138.5 (ArC), 136.6 (ArC), 136.5
[Ni(η5-C5H5)(CH3CN)(Bn2-bimy)]+(ClO4)−
(2i). Obtained (ArC), 129.6 (ArC), 114.1 (q, J = 291.5 Hz, CF3), 91.6 (C5H5), 51.2
from 1e (70.0 mg, 0.153 mmol) and AgClO4 (33.3 mg, (NH2C–CH2N), 21.4 (p-ArCH3), 18.0 (o-ArCH3). 19F NMR
0.160 mmol, 1.05 eq.) in acetonitrile (1.5 mL). Yield: 68%, (376 MHz, CDCl3) δ(ppm): −74.30 (s). EI MS (70 eV) m/z (58Ni):
yellow solid (58.5 mg, 0.104 mmol). 1H NMR (400 MHz, CDCl3) 542 (M+, 17%), 477 ([M − Cp]+, 16), 429 ([M − CF3CO2]+, 26),
δ(ppm): 7.40–7.27 (10H, m, ArH), 7.12 (4H, bd, J = 7.2 Hz, 305 (SIMes+, 100). Anal. Calc. for C28H31F3N2NiO2: C, 61.91;
ArH), 6.46 (2H, bd, CH2), 6.23 (2H, bd, CH2), 5.24 (5H, s, C5H5), H, 5.75; N, 5.16. Found: C, 61.71; H, 5.83; N, 5.18%.
2.14 (3H, s, CH3CN). 13C{1H} NMR (101 MHz, CDCl3) δ(ppm):
[Ni(η5-C5H5)(NO3)(IMes)] (3c). This compound was pre-
174.2 (NCN), 135.7 (ArC), 129.6 (CH3CN), 129.3 (ArC), 128.5 pared similarly as described for 3a from 1a (64.0 mg,
(ArC), 128.2 (ArC), 126.2 (ArC), 124.1 (ArC), 111.5 (ArC), 93.9 0.138 mmol) and AgNO3 (24.0 mg, 0.141 mmol, 1 eq.) in
(C5H5), 53.2 (CH2Ph), 4.4 (CH3CN). Anal. Calc. for toluene–THF (1.8 mL/1.8 mL) with overnight stirring. Yield:
C28H26ClN3NiO4·2H2O: C, 56.17; H, 5.05; N, 7.02. Found: C, 98%, red solid (66.1 mg, 0.135 mmol). 1H NMR (400 MHz,
56.74; H, 4.95; N, 7.23%.
CDCl3) δ(ppm): 7.24 (2H, s, HCvCH), 7.12 (4H, s, m-ArH), 3.53
[Ni(η5-C5H5)(CH3CN)(IMes)]+(NO3)− (2j). This compound (5H, s, C5H5), 2.43 (6H, s, p-ArCH3), 2.16 (12H, s, o-ArCH3).
was prepared according to the general procedure for cationic 1H NMR (400 MHz, C6D6) δ(ppm): 6.86 (4H, s, m-ArH), 6.40
complexes from 1a (150.0 mg, 0.324 mmol) and AgNO3 (2H, s, HCvCH), 2.34 (5H, s, C5H5), 2.15 (6H, s, p-ArCH3), 2.06
(55.5 mg, 0.327 mmol, 1 eq.) in acetonitrile (4.5 mL). Yield: (12H, s, o-ArCH3). 13C{1H} NMR (101 MHz, CDCl3) δ(ppm):
68%, yellow-green solid (116.7 mg, 0.220 mmol). 1H NMR 139.5 (ArC), 136.5 (ArC), 135.5 (ArC), 129.4 (ArC), 126.8
(400 MHz, CD3CN) δ(ppm): 7.42 (2H, s, HCvCH), 7.19 (4H, s, (HCvCH), 97.1 (C5H5), 21.4 (p-ArCH3), 18.1 (o-ArCH3).
m-ArH), 4.77 (5H, s, C5H5), 2.42 (6H, s, p-ArCH3), 2.21(1.6H due 13C NMR (101 MHz, CDCl3) δ(ppm): 139.5 (s, ArC), 136.5 (s,
to exchange with CD3CN, bs, CH3CN), 2.11 (12H, s, o-ArCH3). ArC), 135.5 (s, ArC), 129.4 (d, J = 151.8 Hz, Mes), 126.6 (d, J =
13C{1H} NMR (101 MHz, CD3CN) δ(ppm): 160.0 (NCN), 140.8 195.1 Hz, HCvCH), 96.9 (d, J = 169.3 Hz, C5H5), 21.4 (q, J =
(ArC), 136.8 (ArC), 136.3 (ArC), 130.2 (ArC), 127.0 (HCvCH), 127.3 Hz, p-ArCH3), 18.1 (q, J = 127.5 Hz, o-ArCH3). EI MS
94.24 (C5H5), 21.2 (p-ArCH3), 18.3 (o-ArCH3). Anal. Calc. for (70 eV) m/z (58Ni): 424 ([M − Cp]+, 80%), 378 ([M − Cp − NO2]+,
This journal is © The Royal Society of Chemistry 2014
Dalton Trans., 2014, 43, 5847–5857 | 5855