Dalton Transactions
Paper
Synthesis of 3
6.77–8.06 (m, 13H, Ph), 4.51 (s, 5H, Cp), 3.15 (s, 4H, CH2), 2.07
(broad s, 18H, CH3). 13C NMR (benzene-d6) (20 °C) δ (ppm):
214.5, 184.2, 155.4, 149.2, 144.7, 139.7, 138.8, 138.0, 137.0,
130.3, 129.9, 126.9, 125.3, 122.6, 122.1, 92.2, 51.5, 20.9. EI MS
(70 eV) m/z (rel. int.) (58Ni): 582 (M+, 18%), 429 (C26H31N2Ni+,
21%), 304 (C21H24N2 , 100%), 218 (C15H10N2 , 18%), 154
(C12H10+, 50%). Anal. calcd for C38H40N2Ni: C, 78.23; H, 6.91.
Found: C, 77.94; H, 6.63
360 mg (0.97 mmol) of 9-nickelafluorenyllithium dimethoxy-
ethane complex and 40 mL of THF were placed in a Schlenk
flask, and 329 mg (0.97 mmol) of 1,3-bis(2,4,6-trimethyl-
phenyl)imidazolium chloride was added at room temperature.
The reaction was carried out for 24 hours. The solvent was
removed under vacuum. The orange solid was washed with
hexane and deoxygenated water, and dried under vacuum.
Compound 3 was obtained as an orange solid. Yield: 432 mg
(0.74 mmol, 76%). 1H NMR (acetonitrile-d3) (20 °C) δ (ppm):
+
+
Reaction of 1 in 1,4-dioxane-d8
3
20 mg of 1 and 2 mL of 1,4-dioxane-d8 were placed in a
Schlenk flask. The reaction was refluxed for three hours. The
orange solid was dissolved, and the colour of the solution
changed to olive. After the reaction was completed, the solvent
was removed under vacuum. The olive solid was dissolved in
8.54 (s, 1H, imidazole), 7.66 (s, 2H, vCH), 7.24 (d, J = 7.2 Hz,
2H, Ph), 7.16 (s, 4H, Ph), 6.99 (d, J = 7.2 Hz, 2H, Ph), 6.62 (t,
3
3J = 7.2 Hz, 2H, Ph), 6.35 (t, 3J = 7.2 Hz, 2H, Ph), 5.14 (s, 5H, Cp),
2.39 (s, 6H, CH3), 2.09 (s, 12H, CH3). 13C NMR (acetonitrile-d3)
(20 °C) δ (ppm): 174.33, 156.38, 143.51, 142.63, 135.70, 130.71,
130.13, 125.96, 122.33, 120.33, 118.76, 90.45, 21.61, 17.95.
1
0.6 mL of benzene-d6. H NMR (benzene-d6) (55 °C) δ (ppm):
+
6.77–8.06 (m, 13H, Ph), 4.51 (s, 5H, Cp), 3.15 (s, 4H, CH2), 2.07
(broad s, 18H, CH3).
Electrospray MS (acetone) m/z: 305 (C21H25N2 ). Anal. calcd for
C38H38N2Ni: C, 78.50; H, 6.59. Found: C, 78.87; H, 6.71.
Synthesis of 6
Synthesis of 4
486 mg (0.94 mmol) of 4 and 20 mL of dioxane were placed in
a Schlenk flask. The reaction was refluxed for 48 hours. The
orange solid was dissolved and the colour of the solution
changed to olive. After the reaction was completed, the solvent
was removed under vacuum. The olive solid was washed with
hexane and dried under vacuum. The dark solid was extracted
with two portions (2 × 25 mL) of toluene. The combined
extracts were dried under vacuum. 430 mg (0.83 mmol, 88%)
of 6 was isolated. 1H NMR (acetonitrile-d3) (20 °C) δ (ppm):
6.62–7.31 (m, 11H, Ph), 6.58 (m, 1H, vCH), 6.36 (m, 1H,
vCH), 4.93 (s, 5H, Cp), 3.89 (m, 2H, CH2), 2.37 (s, 3H, CH3),
1.55 (m, 2H, CH2), 1.43 (s, 6H, CH3), 1.40 (m, 2H, CH2), 1.02 (t,
3J = 7.2 Hz, 3H, CH3). 13C NMR (acetonitrile-d3) (20 °C) δ
(ppm): 176.6, 154.7, 150.9, 146.3, 143.2, 139.5, 137.9, 131.1,
129.9, 128.5, 127.7, 126.7, 125.0, 123.8, 122.4, 121.9, 92.3, 51.1,
34.0, 21.6, 21.4, 18.0, 14.7. EI MS (70 eV) m/z (rel. int.) (58Ni):
365 mg (0.98 mmol) of 9-nickelafluorenyllithium dimethoxy-
ethane complex and 30 mL of THF were placed in a Schlenk
flask, and 316 mg (0.98 mmol) of 1-(2,4,6-trimethylphenyl)-3-
(n-butyl)-imidazolium bromide was added at room tempera-
ture. The reaction was carried out for 24 hours. The solvent
was removed under vacuum. The dark-orange solid was
washed with hexane and deoxygenated water, and dried under
vacuum. Compound 4 was obtained as an orange solid. Yield:
1
466 mg (0.90 mmol, 92%). H NMR (THF-d8) (20 °C) δ (ppm):
3
8.33 (s, 1H, imidazole), 7.24 (s, 1H, vCH), 7.03 (d, J = 7.2 Hz,
3
2H, Ph), 6.97 (s, 1H, vCH), 6.91 (s, 2H, Ph), 6.80 (d, J = 7.2
3
3
Hz, 2H, Ph), 6.36 (t, J = 7.2 Hz, 2H, Ph), 6.05 (t, J = 7.2 Hz,
2H, Ph), 4.84 (s, 5H, Cp), 3.50 (2H, CH2), 2.30 (s, 9H, CH3),
3
1.22 (m, 2H, CH2), 0.84 (m, 2H, CH2), 0.70 (t, J = 7.2 Hz, 3H,
CH3). 1H NMR (acetonitrile-d3) (20 °C) δ (ppm): 8.48 (s, 1H,
3
imidazole), 7.56 (s, 1H, vCH), 7.37 (s, 1H, vCH), 7.25 (d, J =
+
518 (M+, 17%), 306 (C21H26N2 , 33%), 243 (C16H23N2+, 100%),
3
7.2 Hz, 2H, Ph), 7.12 (s, 2H, Ph), 7.05 (d, J = 7.2 Hz, 2H, Ph),
154 (C12H10+, 82%). Anal. calcd for C33H36N2Ni: C, 76.32; H,
6.99. Found: C, 76.89; H, 7.17.
6.61 (t, 3J = 7.2 Hz, 2H, Ph), 6.36 (t, 3J = 7.2 Hz, 2H, Ph), 5.12 (s,
3
5H, Cp), 4.13 (t, J = 7.2 Hz, 2H, CH2), 2.38 (s, 3H, CH3), 1.98
3
(s, 6H, CH3), 1.81 (m, 2H, CH2), 1.28 (m, 2H, CH2), 0.95 (t, J = Reaction of 1 with dichloromethane
7.2 Hz, 3H, CH3). 13C NMR (THF-d8) (20 °C) δ (ppm): 174.60,
210 mg (0.36 mmol) of 1 and 40 mL of CH2Cl2 were placed in
156.30, 144.00, 141.57, 138.48, 135.88, 132.79, 130.58, 124.76,
124.18, 122.73, 120.68, 119.33, 90.53, 50.40, 33.75, 21.66,
20.33, 17.92, 14.60. Electrospray MS (acetone) m/z: 243
a Schlenk flask. The reaction was carried out for 7 days at
room temperature. The green–brown solution was filtered and
concentrated to approximately 10 mL. 20 mL of hexane was
added, and a green oil precipitated from the solution. The red
solution was separated, and the green oil was dried under
vacuum. The resulting green solid was washed with toluene
and dried under vacuum. Compound 7 was obtained as a
+
(C16H23N2 ). Anal. calcd for C33H36N2Ni: C, 76.32; H, 6.99.
Found: C, 76.08; H, 7.25.
Synthesis of 5
520 mg (0.89 mmol) of 1 and 20 mL of dioxane were placed in green solid. Yield: 98 mg (0.09 mmol, 75%). 1H NMR (dichloro-
a Schlenk flask. The reaction was refluxed for three hours. The methane-d2) (20 °C) δ (ppm): 7.14 (broad s, 4H, Ph), 6.66
orange solid was dissolved, and the colour of the solution (broad s, 1H, N–CH), 5.81 (broad s, 4H, CH2), 2.52 (broad s,
changed to olive. After the reaction was completed, the solvent 12H, CH3), 2.43 (broad s, 6H, CH3). 13C NMR (dichloro-
was removed under vacuum. The olive solid was washed with methane-d2) (20 °C) δ (ppm): 158.2; 140.0, 134.9, 129.9, 46.1,
hexane and dried under vacuum. 470 mg (0.81 mmol, 91%) of 26.4, 20.5. Crystals were grown from the CH2Cl2–hexane
5 was isolated. 1H NMR (benzene-d6) (55 °C) δ (ppm): system. We are unable to provide elemental analysis for 7
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Dalton Trans.