European Journal of Inorganic Chemistry
10.1002/ejic.201701169
FULL PAPER
Schlenk-type glassware on a dual manifold Schlenk line in a glove
box.[71,72] Nitrogen was deoxygenated using an activated Cu catalyst and
dried with Drierite.[73] All chemicals were purchased from commercial
sources (purity > 99%) and used as received unless otherwise indicated.
All solvents such as toluene and n-hexane, were dried by distillation from
2 2 2
Me). HRMS m/z calcd for [C24H24Cl N O + H] 441.1136. Found:
441.1131.
Data
for
N,N'-(2,3-naphthalene)bis(3,5-dimethylsalicylideneimine)
1
[
(naph)salenH
2
]: orange solid (1.52 g, 72%). H NMR (CDCl
3
): δ 12.9 (br,
2
H, –OH), 8.65 (s, 2H, ArCH=N–), 7.84 (m, 2H, Ar–H), 7.52 (s, 2H, Ar–H),
.47 (m, 2H, Ar–H), 7.07 (s,2H, Ar–H), 7.05 (s,2H, Ar–H), 2.28 (s, 6H,
): δ 164.4 (ArCH=N–),
57.8, 143.2, 135.7, 132.8, 130.1, 127.8, 126.3, 118.4, 117.1 (Ar), 20.48
Ar–Me), 15.70 (Ar–Me). HRMS m/z calcd for [C26 + H] 423.2072.
Found: 423.2067.
General Synthesis of (salen)AlMe Compounds. AlMe
.5 M toluene solution, 0.65 mmol) was added to a stirred solution of the
sodium/benzophenone ketyl or CaH
stored over activated molecular sieves (4 Å). Carbon dioxide (99.999%)
was used as received without further purification. CDCl and C were
2
under a nitrogen atmosphere and
7
Ar–Me), 2.26 (s, 6H, Ar–Me). 13C NMR (CDCl
3
3
6 6
D
1
dried over 4 Å activated molecular sieves and used after vacuum transfer
to a Schlenk tube equipped with a J. Young valve.
(
26 2 2
H N O
Measurements. 1H and 13C NMR spectra were recorded at ambient
3
(0.33 mL of
temperature on
a Bruker DPX-500 MHz NMR spectrometer using
0
standard parameters. All chemical shifts are reported in δ and referenced
corresponding salen ligand (0.5 mmol) in toluene at 0°C. The mixture
was allowed to warm to room temperature and was left to stir overnight.
The volatiles were removed under vacuum, and the residue was
recrystallized from toluene at –15°C to give the desired products.
1
to the residual CDCl
3
(δ 7.24 for H NMR; δ 77.00 for 13C NMR) and C
6 6
D
(
δ 7.16 for 1H NMR; δ 128.06 for 13C NMR). Elemental analyses were
performed with EA 1110-FISONS analyzer. High-resolution mass spectra
(
HRMS) were acquired on a high resolution Q-TOF mass spectrometer
ionization mode: ESI).
Data
for
[ethylenebis(3,5-dimethylsalicylideneiminato)-
(
κN,N',O,O']methylaluminum (III) ((salen)AlMe): ivory solid (0.15 g, 82%).
Synthesis. N,N'-ethylenebis(3,5-dimethylsalicylideneimine) (salenH
was prepared according to the literature procedures.[65]
2
)
1H NMR (C
6
D
6
): δ 7.34 (s, 2H, ArCH=N–), 7.05 (s,2H, Ar–H), 6.58 (s, 2H,
–), 2.58 (s, 6H, Ar–Me), δ2.49 (m, 2H,
–), 2.20 (s, 6H, Ar–Me), –0.44 (s, 3H, Al–Me). 13C NMR (CDCl
): δ
168.3 (ArCH=N–), 163.0, 137.5, 130.8, 129.8, 124.5, 117.6 (Ar), 54.86
(=NCH –), 20.41, 16.14 (Ar–Me). HRMS m/z calcd for [C21
Ar–H), 3.06 (m, 2H, =NCH
2
General Synthesis of Salen Compounds. The appropriate
corresponding diamine (5.0 mmol) was added to a stirred solution of 2–
hydroxy-3,5-dimethylbenzaldehyde (1.50 g, 10.0 mmol) in 20 mL of
ethanol at room temperature. The reaction mixture was allowed to reflux
overnight, cooled, and filtered. The resulting residue was washed with
cold ethanol (3 × 10 mL), and then dried in vacuo to afforded the desired
products.
=NCH
2
3
2
2 2
H25AlN O +
Na] 387.1629. Found: 387.1624. Anal. Calcd for C21
2 2
H25AlN O : C, 69.21;
H, 6.92; N, 7.69. Found: C, 69.16; H, 6.94; N, 7.72.
Data
κN,N',O,O']methylaluminum (III) ([(phen)salen]AlMe): yellow solid (0.20
g, 97%). 1H NMR (C
): δ 8.00 (s, 2H, ArCH=N–), 7.09 (s,2H, Ar–H),
6.90 (m, 2H, Ar–H), 6.82 (m, 2H, Ar–H), 6.95 (s, 2H, Ar–H), 2.61 (s, 6H,
Ar–Me), 2.19 (s, 6H, Ar–Me), –0.40 (s, 3H, Al–Me). 13C NMR (CDCl
): δ
164.1 (ArCH=N–), 161.3, 139.1, 138.8, 131.1, 130.6, 128.3, 125.3, 117.7,
116.1 (Ar), 20.46, 16.16 (Ar–Me). HRMS m/z calcd for [C25
for
[phenylenebis(3,5-dimethylsalicylideneiminato)-
Data for salenH
3.2 (br, 2H, –OH), 8.27 (s, 2H, ArCH=N–), 6.97 (s, 2H, Ar–H), 6.84 (s,
H, Ar–H), 3.90 (s, 4H, =NCH –), 2.22 (s, 6H, Ar–Me),2.21 (s, 6H, Ar–
): δ 166.7 (ArCH=N–), 157.1, 134.5, 129.2, 127.2,
25.7 117.7 (Ar), 60.00 (=NCH –), 20.42 (Ar–Me), 15.55 (Ar–Me).
2
:[65] yellow solid (1.35 g, 83%). 1H NMR (CDCl
3
): δ
6 6
D
1
2
2
3
Me). 13C NMR (CDCl
3
1
2
2 2
H25AlN O +
2 2
Na] 435.1629. Found: 435.1624. Anal. Calcd for C25H25AlN O : C, 72.80;
Data
for
N,N'-phenylenebis(3,5-dimethylsalicylideneimine)
1
H, 6.11; N, 6.79. Found: C, 72.76; H, 6.05; N, 6.88.
[
(phen)salenH
2
]: yellow solid (1.58 g, 85%). H NMR (CDCl
3
): δ 12.9 (br,
2H, –OH), 8.54 (s, 2H, ArCH=N–), 7.31 (m, 2H, Ar–H), 7.18 (m, 2H, Ar–
Data for [(4,5-dimethylphenylene)bis(3,5-dimethylsalicylideneiminato)-
H), 7.05 (s, 2H, Ar–H), 7.00 (s, 2H, Ar–H), 2.26 (s, 6H, Ar–Me), 2.24 (s,
2
κN,N',O,O']methylaluminum (III) ([(Me phen)salen]AlMe): yellow solid
1
6
1
H, Ar–Me). 13C NMR (CDCl
35.2, 129.9, 127.4, 126.1, 121.4, 118.4 (Ar), 20.45 (Ar–Me), 19.62 (Ar–
3
): δ 163.48 (ArCH=N–), 157.6, 140.2, 136.0,
(0.20 g, 91%). H NMR (C
6
D
6
): δ 8.05 (s, 2H, ArCH=N–), 7.10 (s, 2H, Ar–
H), 6.73 (s, 2H, Ar–H), 6.67 (s, 2H, Ar–H), 2.64 (s, 6H, Ar–Me), 2.21 (s,
6H, Ar–Me), 1.98 (s, 6H, Ar–Me), –0.35 (s, 3H, Al–Me). 13C NMR (C
):
δ 164.6 (ArCH=N–), 160.4, 138.6, 137.1, 136.8, 131.3, 130.8, 124.6,
18.0, 117.0 (Ar), 20.50, 19.88, 16.59 (Ar–Me). HRMS m/z calcd for
Na] 463.1942. Found: 463.1937. Anal. Calcd for
: C, 73.62; H, 6.64; N, 6.36. Found: C, 73.67; H, 6.70; N,
Me), 15.65 (Ar–Me). HRMS m/z calcd for [C24
H N O
24 2 2
+ H] 373.1916.
6 6
D
Found: 373.1911.
1
Data for N,N'-(4,5-dimethylphenylene)bis(3,5-dimethylsalicylideneimine)
1
[C27H29AlN
2 2
O +
[
(Me
2
phen)salenH
2
]: yellow solid (1.66 g, 83%). H NMR (CDCl
3
): δ 13.1
C H29AlN O
27 2 2
(
br, 2H, –OH), 8.54 (s, 2H, ArCH=N–), 7.03 (s, 2H, Ar–H), 6.99 (s, 2H,
Ar–H), 6.97 (s, 2H, Ar–H), 2.30 (s, 6H, Ar–Me), 2.26 (s, 6H, Ar–Me), 2.24
s, 6H, Ar–Me). 13C NMR (CDCl
): δ 163.5 (ArCH=N–), 157.6, 140.2,
36.0, 135.2, 129.9, 127.4, 126.1, 121.4, 118.4 (Ar), 20.45 (Ar–Me),
6.42.
(
3
Data for [(4,5-dichlorophenylene)bis(3,5-dimethylsalicylideneiminato)-
1
1
4
2
κN,N',O,O']methylaluminum (III) ([(Cl phen)salen]AlMe): orange solid
1
9.62 (Ar–Me), 15.65 (Ar–Me). HRMS m/z calcd for [C26
H N O
28 2 2
+ H]
(0.21 g, 87%). H NMR (C
6
D
6
): δ 7.58 (s, 2H, ArCH=N–), 7.07 (s, 2H, Ar–
01.2229. Found: 401.2224.
H), 6.84 (s, 2H, Ar–H), 6.56(s, 2H, Ar–H), 2.57 (s, 6H, Ar–Me), 2.18 (s,
H, Ar–Me), –0.45 (s, 3H, Al–Me). 13C NMR (C
): δ 164.7 (ArCH=N–),
161.8, 139.7, 138.4, 132.0, 131.3, 130.7, 125.8, 118.0, 117.5 (Ar), 20.48,
6.11 (Ar–Me). HRMS m/z calcd for [C25 23AlCl + Na] 503.0850.
Found: 503.0844. Anal. Calcd for C25 23AlCl : C, 62.38; H, 4.82; N,
.82. Found: C, 62.44; H, 4.86; N, 5.79.
Data for [(2,3-naphthalene)bis(3,5-dimethylsalicylideneiminato)-
κN,N',O,O']methylaluminum (III) ([(naph)salen]AlMe): orange solid (0.20
6
6 6
D
Data for N,N'-(4,5-dichlorophenylene)bis(3,5-dimethylsalicylideneimine)
1
[
(Cl
2
phen)salenH
2
]: orange solid (1.72 g, 78%). H NMR (CDCl
3
): δ 12.5
1
H
2 2 2
N O
(br, 2H, –OH), 8.51 (s, 2H, ArCH=N–), 7.27 (s, 2H, Ar–H), 7.07 (s, 2H,
Ar–H), 7.00 (s, 2H, Ar–H), 2.26 (s, 6H, Ar–Me), 2.23 (s, 6H, Ar–Me). 13C
H
2 2 2
N O
5
NMR (CDCl
3
, 125.03 MHz): δ 165.2 (ArCH=N–), 157.7, 142.3, 136.3,
130.6, 130.3, 127.8, 126.5, 121.7, 118.0 (Ar), 20.44 (Ar–Me), 15.62 (Ar–
This article is protected by copyright. All rights reserved.