SYNTHESIS OF NEW BULKY BIS(AMIDINE)
289
IR spectra were recorded on a Bruker-Vertex 70 118.6, 122.8, 123.6, 128.3, 128.8, 129.8, 132.5 (C H ,
6
4
instrument. The samples were prepared under dry iso-Pr C H ); 140.3 (NCN).
2
6
3
1
13
7
argon as suspensions in Nujol. H, C, and Li NMR
spectra were detected on Bruker Avance DPX-200 and
Bruker Avance III instruments (400 MHz, 25°С,
C D , pyridine-d , CDCl ). Chemical shifts were pre-
Synthesis of dilithium bis(tetramethylethylenediami-
nate)1,3-phenylenobis{(2,6-diisopropylphenyl)phenyl}ami-
dinate (I). A 1.14 M solution of n-BuLi in hexane (11.2
mL, 12.75 mmol) was added at –70°С to a solution of
compound I (4.05 g, 6.33 mmol) in THF (5 mL). The
temperature of the reaction mixture was slowly
brought to room temperature, and the mixture was
stirred for 2 h. The addition of TMEDA (5 mL) to the
reaction mixture resulted in the precipitation of a yel-
low powder of compound I. The yield was 3.37 g
6
6
5
3
sented in ppm relative to the known shifts of residual
protons of deuterated solvents.
Synthesis of 1,3-phenylenobis{(2,6-diisopropylphe-
nyl)phenyl}amidine (H L). Triethylamine (15.0 mL,
2
1
0.95 g, 108.16 mmol) and then benzoyl chloride
(
12.5 mL, 15.20 g, 108.16 mmol) were poured to a
solution of m-phenylenediamine (5.85 g, 54.08 mmol)
in dichloromethane (100 mL). The reaction mixture
was stirred for 12 h at 40°С and washed with water. The
organic phase was separated and dried over calcined
calcium chloride. The solvents were removed on a
rotary evaporator, and a solid residue was washed and
(
82%). Yellow crystals of complex I were obtained by
the recrystallization of the obtained powder from a
THF–hexane (1 : 5) system.
For C H N Li
2
56 80
8
dried in vacuo at 50°C to a constant weight. The yield Anal. calcd., % C, 76.50
was 15.57 g (91%).
H, 9.17
H, 9.21
N, 12.75
N, 12.81
Found, %
C, 76.72
Phosphorus pentachloride (20.50 g, 98.45 mmol)
was added to a suspension of N,N'-(1,3-phenyl-
ene)dibenzamide (15.57 g, 49.22 mmol) in chloroben-
zene (50 mL), and the mixture was stirred at 60°C.
After the end of hydrogen chloride evolution, the sol-
–1
IR (ν, cm ): 1640 s, 1617 s, 1575 s, 1315 s, 1254 s,
1
221 s, 1103 s, 1037 s, 946 s, 913 s, 865 s, 783 s, 741 s.
Н NMR (400 MHz; 25°C, pyridine-d ; δ, ppm (J,
vent was removed in vacuo and a residue was dissolved Hz)): 0.85 (d, 12H, (CH
1
5
3
)
CH, JH,H = 6.2 Hz); 0.99
3
2
3
in toluene. 2,6-Diisopropylaniline (17.45 g, 98.46 (d, 12H, (CH ) CH, J
= 6.2 Hz); 2.11 (s, 24H,
3
2
H,H
mmol) and Et N (9.96 g, 98.46 mmol) were added to
3
CH , TMEDA); 2.33 (s, 8H, CH , TMEDA); 3.62
3
2
the obtained solution of 1,3-C H {N=C(Ph)Cl}
2
3
6
4
(
2
sept, 4H, (CH ) CH, J = 6.2 Hz); 6.22–7.28 (m,
0H, C H , iso-Pr C H ). Н NMR (400 MHz; 25°C,
3
2
H,H
1
(
17.39 g, 49.22 mmol) in toluene (70 mL). The reac-
6
4
2
6
3
tion mixture was stirred at 110°C for 72 h. The solvent
benzene-d ; δ, ppm (J, Hz)): 1.13, 1.22 (d, 12H,
was removed in vacuo, and a solid residue was dis-
6
3
solved in diethyl ether (100 mL) and washed with a 1% (CH ) CH, JH,H = 6.8 Hz); 1.97 (br.s, 32H,
3
2
aqueous solution of Na CO (3 × 100 mL). The ethe-
3
2
3
TMEDA); 3.60 (sept, 4H, (CH ) CH, JH,H =
.8 Hz); 6.78–7.11 (m, 16H, C H , iso-Pr C H );
.34–7.36 (m, 4H, C H , iso-Pr C H ). C NMR
50 MHz; 2°C, pyridine-d ; δ, ppm): 22.8, 24.7
3 2
real layer was separated and dried over calcined
6
7
(
(
6 4 2 6 3
MgSO . The solvent was removed in vacuo, and a solid
4
13
6 4 2 6 3
residue was recrystallized from hexane. The yield of
bis(amidine) H L as a white amorphous powder was
5
2
(CH ) CH); 27.9 ((CH ) CH); 45.7 (CH , TMEDA);
1
6.87 g (54%).
3 2 3 2 3
5
7.9 (CH , TMEDA); 114.2, 120.6, 122.5, 123.6,
126.9, 130.6, 141.2, 154.9 (C H , iso-Pr C H ); 167.6
(NCN). Li NMR (155.5 MHz; 25°C, pyridine-d ; δ,
2
For C H N
4
4
50
4
6
4
2
6
3
7
Anal. calcd., %
Found, %
C, 83.07
C, 83.38
H, 7.94
H, 8.01
N, 8.82
N, 8.64
5
ppm): 3.3.
The X-ray structure analysis of complex I was car-
Mass spectrum (EI; 70 eV; m/z (I , %)): 634.3
rel
ried out on a Bruker Smart Apex diffractometer
+
–1
[
M] (15). IR (ν, cm ): 3390 s, 1632 s, 1596 s, 1538 s, (ω scan, МоK radiation, λ = 0.71073 Å, T = 150 K).
α
1
1
351 s, 1263 s, 1094 s, 1031 s, 777 s. Н NMR (200 Experimental sets of intensities were integrated,
MHz; 25°C; CDCl ; δ, ppm (J, Hz)): 1.30 (d, 24H,
3
absorption corrections were applied, and the structure
3
(
(
(
CH ) CH, JH,H = 6.9 Hz); 2.96 (sept, 4H, was refined using the SMART [19], TWINABS [20],
3
2
3
CH ) CH, J = 6.9 Hz); 6.08 (br.s, 2H, NH); 6.83 and SHELX [21] program packages. The structure was
3
2
H,H
3
solved by a direct method and refined by full-matrix
t, 2H, iso-Pr C H , J = 7.7 Hz); 7.07 (d, 4H, iso-
2
6
3
H,H
3
2
hkl
Pr C H , J
= 7.7 Hz); 7.14 (br.s, 2H, C H , iso-
2
6
3
H,H
6 4
least squares for F in the anisotropic approximation
3
Pr C H ); 7.21 (d, 4H, C H , iso-Pr C H , J =
for non-hydrogen atoms. Hydrogen atoms were placed
2
6
3
6
4
2
6
3
H,H
6
.1 Hz); 7.34 (s, 5H, C H , iso-Pr C H ); 7.49 (s, 3H, in geometrically calculated positions and refined iso-
6 4 2 6 3
13
C H , iso-Pr C H ). C NMR (100 MHz; 25°C; tropically with fixed thermal parameters U(H)iso
=
6
4
2
6
3
CDCl ; δ, ppm): 22.5 ((CH ) CH); 27.9 ((CH ) CH); 1.2U(C) (U(H) = 1.5U(C) for methyl fragments).
3
3 2
3 2
eq
iso
eq
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 4 2019