O. Mert, A. Kayan / Applied Catalysis A: General 464–465 (2013) 322–331
323
6.80 (d, CH-4, CH-6, Ar), 8.16 (m, CH ), 8.35 (s, Ar-OH). 13C NMR
(CDCl3, ppm), ı: 0.0, −1.99 (CH3 Si), 13.7, 15.1 (CH2 Si), 19.0
(CH3, OEt), 25.1 (CH2), 56.6 (CH3O), 58.57 (SiOCH2), 61.9 (CH2 N),
(98%, Alfa Aesar) was recrystallized with ethyl acetate before use.
All syntheses were carried out in closed vessels under ambient
atmosphere. SPIMP and its derivatives were prepared in a similar
way as in literatures for imine compounds [14,15].
114.3, 117.9, 118.8, 123.4, 149.4 ( COMe, Ar), 153.7
C OH, Ar),
165.3 (CH N). FTIR (KBr pellet, cm−1): 3249 (O H), 3060 (C H,
Ar), 2972, 2928, 2881, 1632 (C N), 1582 (C C), 1497(C C, Ar),
1460, 1414, 1342, 1281 (C O, phenolic), 1259, 1182, 1151, 1001,
1076, 1038, 951, 802, 754, 638, 566.
1
1H and 13C{ H} NMR experiments were carried out with a
Bruker 400 MHz spectrometers. Infrared spectra of complexes were
recorded on Shimadzu 8201/86601 PC spectrometer. The elemental
analyses were carried out on a LECO CHNS-932 elemental analyzer.
Mass spectrometries (SCIEX 4000 QTRAP LC–MS/MS and Waters
SYNAPT, HRMS) were used for measuring the molecular masses
2.3. Preparation of HO-SPIMPH precursor
The reaction of 3-aminopropyldiethoxymethylsilane (2.92 g,
1.47 × 10−2 mol)
with
4-hydroxysalicylaldehyde
(2.08 g,
of precursors and complexes with electrospray ionization (ESI
)
1.47 × 10−2 mol) in ethanol (30 mL) was performed under similar
conditions to the above reaction (2.1). The yellow solid product was
obtained. Elemental analysis for C24H36N2O7Si2 (520.72 g/mol):
Calc. H 6.97, N 5.38%; found: H 7.01, N 5.10%. HRMS (ESI+):
475.1649, Calc. for C22H30N2O6Si2 [M+H+-EtOH] 475.1721. 13C
NMR (CDCl3, ppm), ı: 0.0 (CH3 Si), 13.75 (CH2 Si), 18.4 (CH3,
OEt), 24.0 (CH2), 58.4 (OCH2Si), 65.7 (CH2 N), 114.3, 117.9, 118.8,
123.4, 149.4 (C4 OH, Ar), 153.7 (C2 OH, Ar), 165.31 (CH N). FTIR
(KBr cell, cm−1): 3410 (O H), 3053 (C H, Ar), 2972, 2930, 2880,
1643 (C N), 1539 (C C), 1506, 1470, 1365, 1287 (C O, phenolic),
1259, 1232, 1113, 1078, 1038, 1020, 846, 793, 609.
method. Thermogravimetric analysis was performed on a Perkin
Elmer Pyris 1 TGA. Samples were heated from 25 ◦C to 950 ◦C at
heating rate of 10 ◦C min−1 in nitrogen or synthetic air flow. Dif-
ferential colorimetric measurement (Perkin Elmer DSC 8000) was
used for measuring glass transition temperature (Tg) of copoly-
mer. Samples were heated from −150 ◦C to 20 ◦C at heating rate of
10 ◦C min−1 in helium gas. Gel permeation chromatographic (GPC)
analysis was performed at 30 ◦C on a Shimadzu prominence GPC
system equipped with a RID-10A refractive index detector, a LC-
20AD solvent delivery unit, a CTO-10AS column oven and a set of
two columns, PSS SDV 5 L 1000 A◦ and PSS SDV 5 L 50 A◦. THF
(HPLC grade) was used as the mobile phase at 1.0 mL/min. The
sample concentration was 2 mg/mL, and the injection volume was
50 L. The calibration curve was made with seven polystyrene stan-
dards covering the molecular weight range from 162 to 34,300 Da.
2.4. Preparation of Br-SPIMPH precursor
The
reaction
of
3-aminopropyldiethoxymethylsilane
(1.96 g, 9.92 × 10−3 mol) with 5-bromosalicylaldehyde (2.04 g,
9.92 × 10−3 mol) in ethanol (30 mL) was performed under similar
conditions to the above reaction (2.1). Yield, 98%. The product was
yellow viscous liquid. Elemental analysis for C24H34Br2N2O5Si2
(646.52 g/mol): Calc. C 44.59, H 5.30, N 4.33%; found: C 44.35, H
5.72, N 3.71%. HRMS (ESI+): 600.9908, Calc. for C22H29Br2N2O4Si2
[M+H+-EtOH] 601.00. 1H NMR (CDCl3, ppm), ı: 0.0 (s, Si CH3),
0.43 (t, CH2 Si), 1.10 (t, CH3, OEt), 1.60 (m, CH2), 3.40 (t, CH2 N),
3.61 (q, OCH2, OEt), 5.5 (s, OH Si), 6.7 (d, CH-3, Ar), 7.2 (m, CH-4,
6, Ar), 8.15 (m, CH ), 13.1 (br, s, OH). 13C NMR (CDCl3, ppm), ı:
−3.79, −1.65 (CH3 Si), 12,0 13.7 (CH2 Si), 17.3 (CH3, OEt), 23.2
(CH2), 57.0 (OCH2Si), 60.9 (CH2 N), 108.6 (C Br, Ar) 117.9 (C-3,
Ar), 118.9 (C-1, Ar), 132.1 (C-6, Ar), 133.6 (C-4, Ar) 159.4 (C-OH,
Ar), 162.3 (CH N). FTIR (KBr cell, cm−1): 3387(O H), 3061 (C H,
Ar), 2972, 2930, 2881, 1634 (C N), 1607, 1574 (C C), 1479 (C C,
Ar), 1443, 1391, 1366, 1342, 1279 (C O, phenolic), 1259, 1198,
1180, 1167, 1105, 1078, 951, 877, 820, 800, 764, 627.
2.1. Preparation of SPIMPH precursor
3-Aminopropyldiethoxymethylsilane (3.3 g, 1.67 × 10−2 mol)
was added to the stirring solution of salicylaldehyde (2.08 g,
1.67 × 10−2 mol) in ethanol (30 mL) in the presence of a few drops
of formic acid, which was let to react for overnight at room tem-
perature. After that, anhydrous Na2SO4 was added and kept in
the solution for a few minutes to absorb water. Then, Na2SO4
was removed from the solution by filtration. The volatile parts
of the resulting solution were removed under reduced pressure.
The yellow viscous liquid product was obtained. Elemental analysis
for C24H36N2O5Si2 (488.72 g/mol): Calc. C 58.98, H 7.42, N 5.73%;
found: C 57.78, H 7.14, N 5.31%. HRMS (ESI+): 443.1748, Calc. for
C22H30N2O4Si2 [M+H+-EtOH] 443.1822. 1H NMR (CDCl3, ppm), ı:
0.0 (s, Si-CH3), 0.42 (t, CH2 Si), 1.10 (t, CH3, OEt), 1.60 (m, CH2),
3.40 (t, CH N), 3.60 (q, OCH2, OEt), 6.7 (dt, CH-3,5, Ar), 7.1 (dt,
CH-4,6, Ar), 8.15 (m, CH ), 13.3 (s, OH). 13C NMR (CDCl3, ppm),
ı: 0.0, −1.6 (CH3 Si), 15.3 (CH2 Si), 18.8 (CH3, OEt), 24.9 (CH2),
58.6 (SiOCH2), 62.3 (CH2 N), 117.4, 118.8, 119.2, 131.6, 132.4 ( C,
2.5. Preparation of (SPIMP)2Zr2(OnPr)2O compound
Ar), 161.8
C
OH, Ar), 165.1 (CH N). FTIR (KBr cell, cm−1): 3252
SPIMPH (1.26 g, 2.57 × 10−3 mol) was added to the solution
of zirconium n-propoxide (1.0 g, 2.13 × 10−3 mol) in 20 mL n-
propanol. The reaction mixture was stirred for 3 hours at room
temperature. Then, the volatile parts were removed from the solu-
tion by vacuum evaporator at 30 ◦C. After that, the yellow solid
product was washed three times with hexane and dried under
reduced pressure. Elemental analysis (dimer, C54H82N4O13Si4Zr2,
(SPIMP)2Zr2(OnPr)2O, Mw = 1290.04 g/mol): Calc. C 50.28, H 6.41, N
4.34%. Found: C, 50.40, H 6.21, N, 4.31%. HRMS (ESI+): 1242.3734,
Calc. for C52H76N4O12Si2Zr2 [M+H+-EtOH] 1242.2709. 1H NMR
(CDCl3, ppm) ı: 0.0 (s, Si CH3), 0.52 (t, CH2 Si), 0.8 (t, CH3, OnPr),
1.15 (t, CH3, OEt), 1.5 (t, OnPr), 1.60 (m, CH2), 3.45 (t, CH2 N, OCH2,
OnPr), 3.60 (q, OCH2, OEt), 6.7 (t, CH-5, Ar), 6.8 (d, CH-3), 7.2 (m, CH-
4, 6, Ar), 8.15 (s, CH ). 13C NMR (CDCl3, ppm), ı: 0.0, −1.6 (CH3 Si),
10.1 (CH3, OnPr), 14.1 (CH2 Si), 18.4 (CH3, OEt), 22.6, 25.9 (CH2),
29.7 (CH2, OnPr), 31.6, 57.5 (SiOCH2), 64.7 (CH2 N), 117.4, 118.4,
(O H), 3061 (C H, Ar), 2972, 2928, 2881, 1632 (C N), 1582 (C C),
1497 (C C, Ar), 1460, 1445, 1391, 1377, 1342, 1281 (C O, pheno-
lic), 1259, 1182, 1165, 1151, 1076, 1038, 1020, 951, 872, 802, 754,
640, 566, 460, 424.
2.2. Preparation of MeO-SPIMPH precursor
The
reaction
of
3-aminopropyldiethoxymethylsilane
(2.59 g, 1.29 × 10−2 mol) with 3-methoxysalicylaldehyde (2.0 g,
1.29 × 10−2 mol) in ethanol (30 mL) was carried out under similar
conditions to the preceding reaction (2.1). Yield, 91%. The product
was yellow viscous liquid. Elemental analysis for C26H40N2O7Si2
(548.78 g/mol): Calc. C 56.90, H 7.35, N 5.10%; found: C 56.50, H
7.22, N 4.96%. HRMS (ESI+): 503.1954, Calc. for C24H34N2O6Si2
[M+H+-EtOH] 503.2034. 1H NMR (CDCl3, ppm), ı: 0.0 (s, Si CH3),
0.50 (t, CH2 Si), 1.12 (t, CH3, OEt), 1.60 (d, CH2 and HO Si), 3.45
(t, CH2 N), 3.61 (q, CH2, OEt), 3.83 (s, OCH3), 6.65 (t, CH-5, Ar),
119.2, 131.1, 132.0 ( C, Ar), 161.8 (
C OH, Ar), 165.0 (CH N). FTIR
(KBr cell, cm−1): 3445 (O H, Si OH), 3061 (C H, Ar), 2959, 2924,