Inorganic Chemistry
Article
observed in the H NMR spectrum. The 13C NMR spectrum (see the
SI) is too complicated to do a full assignment of both isomers
separately.
1
[
nBu N][PF ] as the supporting electrolyte. Data were recorded with
4 6
Autolab NOVA software (version 1.8). UV−vis spectra were recorded
−5
in a THF solution (∼10 M) using a Avantes AvaSpec 3648
spectrometer and an AvaLight-DHS light source inside a N2
atmosphere glovebox. Elemental analyses were performed at the
Microanalytical Department of the University of Groningen or Kolbe
1
Major Isomer (6a). H NMR (C D , 400 MHz, 25 °C): δ 8.09 (d,
2H, J = 8.0 Hz, p-tolyl CH), 7.22−7.09 (overlapped m, 2H, p-tolyl
CH), 6.42 (s, 2H, Mes CH), 2.14 (s, 3H, p-tolyl p-CH ), 1.98 (s, 9H,
6
6
3
19
Microanalytical Laboratory (Mu
̈
lheim an der Ruhr, Germany).
Mes o-CH , p-CH ). F NMR (375 MHz, C D , 25 °C): δ −152.7 (d,
3
3
6
6
[
MesNNC(p-tolyl)NNPh] Zn ([L3] Zn, 3). A 1.2 M solution of
2F, J = 18.0 Hz, C F o-CF), −160.7 (t, 1F, J = 21.9 Hz, C F p-CF),
2
2
6
5
6 5
ZnMe in toluene (1.0 mL, 1.2 mmol) was added slowly to a solution
−163.3 (td, 2F, J = 21.9 and 4.1 Hz, C F m-CF).
2
6 5
1
of L3H (855.5 mg, 2.4 mmol) in toluene (20 mL) at room
temperature. The mixture was stirred for 5 h, after which the volatiles
were removed in vacuo. The residue was subsequently extracted into
hot hexane (15 mL). Slow cooling of the clear dark-purple solution to
Minor Isomer (6b). H NMR (C D , 25 °C): δ 8.25 (d, 2H, J = 8.0
6 6
Hz, p-tolyl CH), 7.87 (d, 2H, J = 8.0 Hz, p-tolyl CH), 7.22−7.09
(overlapped m, 4H, 2 × p-tolyl CH), 6.37 (bs, 2H, Mes CH), 6.31 (bs,
2H, Mes CH), 2.20 (s, 3H, p-tolyl p-CH ), 2.14 (s, 3H, p-tolyl p-CH ),
3
3
−
30 °C for 2 days afforded 609 mg of dark crystals of 3 (0.78 mmol,
1.98 (s, 6H, Mes o-CH ), 1.94 (s, 3H, Mes p-CH ), 1.89 (s, 3H, Mes
p-CH ), 1.87 (s, 6H, Mes o-CH ). F NMR (375 MHz, C D , 25 °C):
3 3 6 6
3
3
1
19
6
5%). H NMR (400 MHz, C D , 25 °C): δ 8.25 (d, 2H, J = 8.4 Hz, p-
6
6
tolyl CH), 7.70 (dd, 2H, J = 8.4 and 1.2 Hz, Ph o-H), 7.20 (d, 2H, J =
δ −153.0 (d, 2F, J = 19.3 Hz, C F o-CF), −156.3 (d, 2F, J = 21.9 Hz,
6
5
8
.0 Hz, p-tolyl CH), 6.92 (t, 2H, J = 8.0 Hz, Ph m-H), 6.76 (t, 1H, J =
C F o-CF), −160.7 (t, 1F, J = 21.9 Hz, C F p-CF), −162.8 (td, 2F, J
6
5
6 5
7
.4 Hz, Ph p-H), 6.38 (s, 2H, Mes CH), 2.20 (s, 3H, p-tolyl CH ), 1.97
= 22.0, 4.7 Hz, C F m-CF), −165.3 (td, 2F, J = 21.6 and 4.1 Hz, C F
3
6
5
6 5
13
(
s, 3H, Mes p-CH ), 1.88 (bs, 6H, Mes o-CH ). C NMR (100 MHz,
m-CF), −167.6 (t, 1F, J = 21.7 Hz, C F p-CF).
3
3
6 5
Trace Isomer (6c). 19F NMR (375 MHz, C D , 25 °C): δ −155.2
C D , 25 °C): δ 152.9 (Ph ipso-C), 148.7 (Mes ipso-C), 144.4 (NCN),
6
6
6
6
1
37.4 (p-tolyl ipso-C), 137.1 (p-tolyl CMe), 130.0 (Ph m-CH), 129.8
(bs, 2F, C F o-CF), −164.2 (t, 2F, J = 20.3 Hz, C F m-CF), −167.3
6
5
6 5
13
(p-tolyl CH), 128.0 (Ph p-CH), 126.5 (p-tolyl CH), 121.5 (Ph o-CH),
(t, 1F, J = 23.5 Hz, C F p-CF). C NMR (100 MHz, C D , 25 °C): δ
6
5
6
6
2
1
1.6 (p-tolyl CH ). Anal. Calcd for C H N Zn: C, 71.17; H, 5.97; N,
4.43. Found: C, 71.16; H, 6.06; N, 13.82.
MesNNC(p-tolyl)NNMes] Zn ([L4] Zn, 4). A 1.2 M solution of
152.3, 149.7 (p-tolyl ipso-C, 6b), 148.1 (Mes ipso-C, 6a), 147.8, 146.5
(p-tolyl ipso-C, 6b), 146.0 (p-tolyl ipso-C, 6a), 141.9 (dm, J = 250.4
Hz, C F ), 141.4 (dm, J = 250.7 Hz, C F ), 139.0 (p-tolyl p-C, 6b),
3
46 46
8
[
2
2
6
5
6 5
ZnMe (101.9 μL, 0.122 mmol) in toluene was added to an orange
138.9, 138.7 (p-tolyl p-C, 6b), 138.7, 138.6 (dm, J = 249.3 Hz, C F ),
2
6 5
solution containing L4H (97.5 mg, 0.245 mmol) in toluene. The
mixture was stirred overnight at 80 °C, after which the solvent was
removed in vacuo to give 57.3 mg of compound 4 as a sticky powder
138.5 (p-tolyl p-C, 6a), 135.6, 135.1, 131.9, 131.5, 131.5, 130.5 (Mes
m-C, 6a), 130.1 (Mes m-C, 6b), 129.8, 129.7, 129.5, 128.9 (p-tolyl
CH, 6b), 128.5, 128.3, 126.4 (p-tolyl CH, 6b), 126.1 (p-tolyl CH, 6a),
126.0, 21.6, 21.6 (p-tolyl p-CH , 6b), 21.5 (Mes p-CH , 6b), 21.3,
(
0.067 mmol, 54% yield). Recrystallization by the slow diffusion of
3
3
pentane into a toluene solution afforded orange crystalline material
21.0, 20.9, 20.7 (Mes p-CH , 6b), 18.3, 17.9 (Mes o-CH , 6b). Anal.
3
3
1
(
16.9 mg, 0.020 mmol, 16% yield). H NMR (C D , 25 °C, 500
Calcd for C H F N Zn: C, 57.78; H, 3.79; N, 11.72. Found: C,
6
6
46 36 10 8
MHz): δ 8.04 (d, 4H, J = 7.8 Hz, p-tol o-H), 7.08 (d, 4H, J = 7.8 Hz, p-
58.66; H, 4.00; N, 11.13.
tol m-H), 6.59 (s, 8H, Mes m-H), 2.11 (s, 6H, p-tol CH ), 2.08 (s,
[PhNNC(p-tolyl)NNPh][MesNNC(CN)NNMes]Zn ([L1][L8]Zn,
8). A flask was charged with [PhNNC(p-tol)NNPh]ZnMe (783 mg,
2.0 mmol), L8H (663 mg, 2.0 mmol), and toluene (20 mL). The
reaction mixture was stirred at room temperature for 2 h, after which
the volatiles were removed in vacuo, and the residue was subsequently
extracted into a hot 1:1 hexane/toluene mixture. Slow cooling of the
clear dark-purple solution to −30 °C for 2 days afforded 796 mg of
dark-violet crystals of 8 (1.12 mmol, 56%). NMR analysis shows the
presence of two isomers in solution. The 13C NMR spectrum (see the
SI) is too complicated to do a full assignment of both isomers
3
13
1
1
1
2H, Mes p-CH ), 1.88 (s, 24H, Mes o-CH ). C NMR (C D , 25 °C,
26 MHz): δ 149.08 (Mes ipso-C), 145.31 (NCN), 137.28 (p-tol p-C),
36.69 (Mes p-C), 136.66 (p-tol ipso-C), 132.64 (Mes o-C), 130.20
3 3 6 6
(
Mes m-CH), 129.85 (p-tol m-CH), 125.65 (p-tol o-CH), 21.48 (p-tol
CH ), 21.15 (Mes p-CH ), 18.29 (Mes o-CH ). Anal. Calcd for
3
3
3
C H N Zn: C, 72.58; H, 6.79; N, 13.02. Found: C, 73.13; H, 6.87;
5
2
58
8
N, 13.17.
C F NNC(p-tolyl)NNPh] Zn ([L5] Zn, 5). A 1.2 M solution of
[
6
5
2
2
ZnMe in toluene (0.29 mL, 0.35 mmol) was added slowly to a
2
solution of L5H (273.8 mg, 0.68 mmol) in toluene (15 mL) at room
temperature. The mixture was stirred overnight, after which the
volatiles were removed in vacuo to afford 237.2 mg of dark crystals of
separately.
1
Major Isomer (8a). H NMR (400 MHz, C
D
6
, 25 °C): δ 7.98 (d,
6
2H, J = 8.4 Hz, p-tolyl CH), 7.51 (d, 4H, J = 8.4 Hz, Ph o-H), 7.21 (d,
2H, J = 8.0 Hz, p-tolyl CH), 6.95 (t, 4H, J = 8.0 Hz, Ph m-H), 6.85 (t,
2H, J = 7.6 Hz, Ph p-H), 6.55 (s, 2H, Mes m-CH), 6.32 (s, 2H, Mes m-
5
(0.27 mmol, 80%). The product thus obtained was ca. 95% pure.
Further purification by recrystallization was not successful. H NMR
1
(
(
6
2
400 MHz, C D , 25 °C): δ 8.22 (d, 2H, J = 8.4 Hz, p-tolyl CH), 7.50
CH), 2.24 (s, 3H, Mes p-CH ), 2.21 (s, 6H, Mes o-CH ), 1.94 (s, 3H,
3
3
6
6
d, 2H, J = 7.6 Hz, Ph o-CH), 7.19 (d, 2H, J = 8.0 Hz, p-tolyl CH),
p-tolyl CH ), 1.59 (s, 3H, Mes p-CH ), 1.56 (s, 6H, Mes o-CH ).
3
3
3
1
.75 (t, 2H, J = 7.6 Hz, Ph m-CH), 6.67 (t, 1H, J = 7.6 Hz, Ph p-CH),
Minor Isomer (8b). H NMR (400 MHz, C
6
D
6
, 25 °C): δ 8.14 (d,
.16 (s, 3H, p-tolyl CH3). 19F NMR (375 MHz, C D , 25 °C): δ
2H, J = 8.4 Hz, p-tolyl CH), 7.33 (d, 4H, J = 7.6 Hz, Ph o-CH), 7.19−
7.13 (m, 2H, p-tolyl CH), 6.98−6.92 (m, 4H, Ph m-CH), 6.80 (t, 2H, J
= 7.4 Hz, Ph p-H), 2.18 (s, 3H, Mes p-CH ), 1.94 (s, 3H, p-tolyl CH ),
6
6
−
154.4 (dd, 2F, J = 22.5, 5.6 Hz, C F o-CF), −158.3 (t, 1F, J = 21.5
6
5
13
Hz, C F p-CF), −162.4 (td, 2F, J = 22.1, 5.2 Hz, C F m-CF).
C
6
5
6
5
3
3
1.84 (s, 6H, Mes o-CH3). 13C NMR (100 MHz, C D , 25 °C): δ 152.4
NMR (100 MHz, C D , 25 °C): δ 151.7 (Ph ipso-C), 145.7 (NCN),
6
6
6 6
1
41.1 (dm, J = 255 Hz, C F ), 138.6 (dm, J = 256 Hz, C F ), 137.8 (p-
(Ph ipso-C, 8b), 151.9 (Ph ipso-C, 8a), 150.9 (Mes ipso-C, 8a), 146.4
(Mes ipso-C, 8b), 145.5 (Mes ipso-C, 8a), 143.3, 142.4 (p-tolyl ipso-C,
8a), 138.3 (Mes p-C, 8a), 137.6 (Mes ipso-C, 8b), 136.8, 136.6 (Mes
p-C, 8a), 136.0 (p-tolyl p-C, 8a), 131.4, 130.9 (Mes p-C, 8a), 130.6
(Mes m-CH, 8a), 130.0 (Mes m-CH, 8b), 129.8 (Mes m-CH, 8a),
129.4 (Ph m-H, 8a), 129.3, 129.0 (p-tolyl CH, 8b), 128.8, 128.2 (Ph p-
H, 8b), 127.8, 127.5, 126.4, 125.8 (p-tolyl CH, 8a), 125.8 (p-tolyl CH,
8b), 125.5, 120.0 (p-tolyl CH, 8b), 119.6 (Ph o-H, 8a), 117.9, 113.0,
20.8 (Mes p-CH , 8a), 20.3, 20.3 (Mes o-CH , 8b), 20.1 (Mes p-CH ,
6
5
6 5
tolyl ipso-C), 137.7 6 (dm, J = 255 Hz, C F ), 135.6 (p-tolyl p-C),
1
CH), 120.5 (Ph o-C), 120.4 (C F ipso-C), 20.8 (p-tolyl CH ).
6
5
29.6 (Ph m-C), 129.5 (Ph p-C), 129.4 (p-tolyl CH), 125.8 (p-tolyl
6
5
3
[
C F NNC(p-tolyl)NNMes] Zn ([L6] Zn, 6). A 1.2 M solution of
6 5 2 2
ZnMe2 in toluene (0.5 mL, 0.6 mmol) was added slowly to a
suspension of L6H (536 mg, 1.2 mmol) in toluene (20 mL) at room
temperature. The mixture was stirred overnight, after which the color
had changed to intense purple. The volatiles were removed in vacuo,
and the residue was subsequently extracted into a hot 3:1 hexane/
toluene mixture. Slow cooling of the clear dark-purple solution to −30
3
3
3
8a), 19.5 (Mes o-CH , 8a), 18.0 (Mes o-CH , 8b), 17.0 (Mes o-CH ,
3
3
3
8a). Anal. Calcd for C H N Zn: C, 67.55; H, 5.53; N, 17.73. Found:
40
39
9
°
C for 2 days afforded 407 mg of dark-violet crystals of 6 (0.43 mmol,
7
C, 67.79; H, 5.58; N, 17.24.
[PhNNC(p-tolyl)NNHPh]Zn(C F ) ([L1H]Zn(C F ) , 9). Toluene
1%). NMR analysis shows the presence of two predominant isomers
5
5 2
5 5 2
19
in solution; an additional isomer (<5%) was observed in the F NMR
spectrum, but resonances due to this species could not be separately
(3 mL) was added onto a mixture of Zn(C F ) (100 mg, 0.25 mmol)
6 5 2
and PhNNC(ptol)NNHPh (78.7 mg, 0.25 mmol). An immediate
H
dx.doi.org/10.1021/ic5025873 | Inorg. Chem. XXXX, XXX, XXX−XXX