Chemistry - A European Journal
10.1002/chem.201802138
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stirred at room temperature for 30 minutes. The volatiles of the
solution were removed under vacuum. The residue was added
by 2 mL of n-pentane and the mixture was stored at -35 °C
overnight. Dark purple solid separated out and was collected by
removing the supernatant. The solid was washed with 2 mL of
cold n-pentane and dried under vacuum to give 2 as a dark
purple solid (90 mg). n-Pentane solutions were combined
together and reduced to 0.5 mL. Crystallization from the n-
pentane solution at -35 °C gave another crop of 2 (8 mg). Total
yield of 2 is 89%. Single crystals of 2 were obtained by cooling a
21.2, 19.8 (br) (CH
7.31; N, 7.81. Found: C, 79.19; H, 7.36; N, 7.56.
3 78 6 2
). Anal. Calcd for C72H N Mg : C, 80.37; H,
Syntheses of 5: Toluene solution (1 mL) of 3 (16.5 mg, 0.015
mmol) stood at 75 °C for 24 hours. The volatiles of the solution
were removed under vacuum to give 5 as a pale pink solid (15.9
mg, 99%) without further purification. Single crystals of 5 were
obtained by slow evaporation of a n-pentane solution with drops
1
of toluene at room temperature. H NMR (400 MHz, C6D6): 7.45
(
d, 3JH-H = 7.2 Hz, 4H, Ar-H), 7.26 (t, 3JH-H = 7.2 Hz, 4H, Ar-H),
7
2
.16 (m, overlapped with C
H, MeC(N)CH), 2.18 (s, 12H, CH
). 13C NMR (100 MHz, C
46.5, 143.4, 137.3 (br), 132.4, 131.6, 131.0 (br), 129.5, 123.3
6
D
6
, Ar-H), 6.46 (s, 8H, Ar-H), 5.17 (s,
), 1.79 (br, 24H, CH3), 1.52
): 168.3 (MeC(N)CH),
1
saturated n-pentane solution at -35 °C. H NMR (600 MHz,
4
3
C
6
D
6
): 7.27 (br, 4H, Ar-H), 7.06 (m, 8H, Ar-H), 6.97 (t, JH-H = 7.2
(
s, 12H, CH
3
6 6
D
4
Hz, 2H, Ar-H), (t, JH-H = 7.2 Hz, 2H, Ar-H), 6.84 (br, 4H, Ar-H),
1
6
2
.77 (s, 4H, Ar-H), 6.76 (s, 4H, Ar-H), 4.95 (s, 2H, MeC(N)CH),
.19 (s, 12H, CH ), 1.91 (s, 12H, CH ), 1.83 (s, 12H, CH ), 1.60
). 13C NMR (151 MHz, C
): 168.8 (MeC(N)CH),
45.0, 142.4, 137.9, 133.1, 131.9, 131.8, 129.4, 129.2, 128.8,
28.7, 128.3, 126.8, 125.8, 124.4 (Ar-C and Ph CN), 96.3
), 34.5, 22.7, 14.3 (n-
: C, 78.33; H, 7.12; N,
(
2
C
7
br), 119.1 (br) (Ar-C and Fluorene-9C), 95.2 (MeC(N)CH), 23.3,
1.3, 19.4 (CH ), 34.5, 22.7, 14.3 (n-pentane-C). Anal. Calcd for
Mg : C, 80.67; H, 6.96; N, 7.84. Found: C, 78.88; H,
.27; N, 7.53.
3
3
3
3
(
s, 12H, CH
3
6 6
D
72
H
74
N
6
2
1
1
2
(
MeC(N)CH), 23.1, 20.9, 19.7, 18.9 (CH
3
Syntheses of 6: Toluene solution (0.6 mL) of 2 (16.6 mg, 0.015
mmol) was sealed in a J-Young NMR tube and frozen in liquid
pentane-C). Anal. Calcd for C72
H
78
N
8
Mg
2
10.15. Found: C, 79.17; H, 6.93; N, 9.35.
nitrogen. The N atmosphere was removed under vacuum and
2
2
and replaced with 2.0 atm O and the solution was warmed to
room temperature. The volatiles of the solution were removed
under vacuum. The residue was washed by n-pentane (2 mL ×
Syntheses of 3: Toluene solution (1 mL) of 9-diazofluorene (40
mg, 0.21 mmol) was added to toluene solution (1 mL) of
[
2
(NacNacMes)Mg] 1 (72 mg, 0.20 mmol), and the mixture was
2
) and dried under vacuum to give 6 as a pale yellow solid (5.1
mg, 88%). Single crystals of were obtained by slow
evaporation of a bzenzene solution at room temperature. 1H
NMR (400 MHz, CDCl ): 7.73 (m, 4H, Ph-H), 7.50-7.32 (m, 12H,
Ph-H), 7.23 (m, 4H, Ph-H). 13C NMR (100 MHz, CDCl
): 169.8
C=N), 137.2, 134.8, 131.6, 130.3, 130.1, 129.9, 128.4, 128.1
Ph-C).
stirred at room temperature for 30 minutes. The volatiles of the
solution were removed under vacuum. The residue was added
by 2 mL of n-pentane and the mixture was stored at -35 °C
overnight. A dark golden solid separated out and was collected
by removing the supernatant. The solid was washed with 2 mL
of cold n-pentane and dried under vacuum to give 3 as a dark
golden solid (58 mg). n-Pentane solutions were combined
together and reduced to 0.5 mL. Crystallization from evaporation
of the n-pentane solution at room temperature gave another
crop of 3 (44 mg). Total yield of 3 is 93%. Single crystals of 3
were obtained by slow evaporation of a n-pentane solution at
6
3
3
(
(
Syntheses of 7: Benzene solution (0.6 mL) of 3 (16.5 mg, 0.015
mmol) was sealed in a J-Young NMR tube and frozen by liquid
nitrogen. The N atmosphere was removed under vacuum and
2
and replaced with 2.0 atm O and the solution warmed to room
2
1
3
room temperature. H NMR (400 MHz, C6D6): 7.76 (dd, JH-H
=
temperature. The volatiles of the solution were removed under
1
7
1.6 Hz, 3
.15 (m, overlapped with C
J
H-H = 7.6 Hz, 4H, Ar-H), 7.39-7.18 (m, 10H, Ar-H),
, 2H, Ar-H), 6.50 (d, 4JH-H = 4.4
), 1.94
). 13C NMR (100 MHz, C
vacuum. The residue was added by a few drops of toluene and
washed by n-hexane (2 mL × 2) and dried under vacuum to give
7 as a pale orange solid (3.8 mg, 72%). Single crystals of 7 were
obtained by slow evaporation of a bzenzene solution at room
6
D
6
Hz, 8H, Ar-H), 5.15 (s, 2H, MeC(N)CH), 1.97 (s, 24H, CH
3
(
s, 12H, CH
3
), 1.70 (s, 12H, CH
3
6 6
D ,
1
3
25 °C): 169.6 (MeC(N)CH), 143.6, 137.5, 136.6, 135.4, 133.6,
131.5, 131.2, 131.1, 129.6, 129.3, 127.1, 126.4, 125.0, 124.1,
122.9, 120.3, 120.1, 117.4 (Ar-C and Fluorene-9C), 95.7
3 H-H
temperature. H NMR (400 MHz, CDCl ): 8.20 (d, J = 7.6 Hz,
2H, Ar-H), 8.07 (d, 3J = 7.6 Hz, 2H, Ar-H), 7.59 (d, 3JH-H = 7.2
Hz, 4H, Ar-H), 7.48 (t, 3J = 7.6 Hz, 2H, Ar-H), 7.43 (t, 3J
7.6 Hz, 2H, Ar-H), 7.36 (t, J
= 7.6 Hz, 2H, Ar-H). 13C NMR (100 MHz, CDCl ): 165.5 (C=N),
H-H
H-H
3
H-H
=
= 7.6 Hz, 2H, Ar-H), 7.24 (t, 3JH-H
(
C
MeC(N)CH), 22.9, 20.8, 19.6, 18.7 (CH
3
). Anal. Calcd for
72 74 8 2
H N Mg : C, 78.61; H, 6.78; N, 10.19. Found: C, 78.27; H,
H-H
3
6
.88; N, 10.15.
143.4, 142.6, 136.3, 133.1, 133.0, 132.7, 131.6, 128.8, 128.7,
+
1
3
24.9, 120.4, 120.3 (Ar-C). MS (DART) [M+1] C26
57.13917 m/z, found 357.14016 m/z.
H
17
N
2
calc.
Syntheses of 4: Toluene solution (1 mL) of 2 (16.6 mg, 0.015
mmol) stood at 50 °C for 12 hours. The volatiles of the solution
were removed under vacuum to give 4 as a yellow solid (16.0
mg, 99%) without further purification. Single crystals of 4 were
obtained by slow evaporation of a n-pentane solution at room
Syntheses of 8: A C D solution (0.6 mL) of 2 (16.6 mg, 0.015
6
6
mmol), Me SiOSO CF
3
3
2
(8.0 mg, 0.036 mmol) and
diphenylmethane (22.7 mg, 0.135 mmol) was sealed in a NMR
tube and the solution stood at room temperature for 1 hour. The
temperature. 1H NMR (400 MHz,
overlapped with C , 28H, Ar-H), 4.88 (s, 2H, MeC(N)CH), 2.31
), 1.66 (br, 24H, CH ), 1.40 (s, 12H, CH
). 13C NMR
100 MHz, C ): 167.7 (MeC(N)CH), 147.3, 132.4 (br), 132.2,
29.7 (br), 128.2 (Ar-C and Ph CN), 97.3 (MeC(N)CH), 23.5,
6 6
C D ): 8.27-5.75 (m/br,
1
6
D
6
H NMR spectrum of the reaction solution was recorded and the
(
(
s, 12H, CH
3
3
3
yield of 8 (86%) was referenced to diphenylmethane. The
generation of 8 was confirmed by HRMS: (DART) [M+1]
6
D
6
+
1
2
C H NSi calc. 254.13650 m/z, found 254.13738 m/z.
1
6
20
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