Supplementary Material
Catalytic activity of an iron(III) schiff base complex bound in a polymer resin
Sk. Manirul Islama,*, Sumantra Paula, Anupam Singha Roya,
Satabdi Banerjeeb, Kajari Ghosha , Ram Chandra Deya, S. C. Santrab
aDept.
bDept.
of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India.
of Env. Science, University of Kalyani, Kalyani, Nadia, 741235, W.B., India
Corresponding author’s E-mail: manir65@rediffmail.com
Figure S1. FE-SEM images of polymer supported Schiff base ligand (A) and polymer-anchored
iron(III)-ferrocene Schiff base complex (B).
1
Figure S2. EDAX images of polymer supported ligand (3) (A) and polymer-anchored iron(III)ferrocene Schiff base complex (B).
2
Table S1. Oxidation of adamantane using different oxidants and solvents catalyzed by polymeranchored iron Schiff base complex.
Entry
Solvent
Oxidant
Yield of adamantine-1-ola (%)
1
CH3CN
NaOCl
17
2
CH3CN
NaIO4
26
3b
CH3CN
H2O2
31
4c
CH3CN
H2O2
78
5d
CH3CN
H2O2
80
6e
CH3CN
H2O2
39
7
CH3CN
TBHP
21
8
CH3CN
KHSO5
21
9
CH3CN
AcOH
29
10
CH3OH
H2O2
38
11
CH3CH2OH
H2O2
33
12
Isopropanol
H2O2
27
Conditions: adamantane (5 mmol); oxidant (10 mmol); CH3CN (10 mL); 50 mg catalyst at 60 0C
for 10 hr. aYield refers to GC & GC-MS analysis. b5 mmol 30% H2O2 was used. c10 mmol 30%
H2O2 was used. d15 mmol 30% H2O2 was used. e25 mmol 30% H2O2 was used.
3
Table S2. Oxidation of styrene using different oxidants and solvents catalyzed by polymeranchored iron(III)-ferrocene Schiff base complex
Run
Solvent
Oxidant
Yield of PhCHO (%)a
1b
CH3CN
H2O2
41
2c
CH3CN
H2O2
91
3
CH3CH2CN
H2O2
76
4
MeOH
H2O2
74
5
EtOH
H2O2
69
6
t
BuOH
H2O2
61
7
DMSO
H2O2
93
8d
CH3CN
H2O2
62
Conditions: styrene (5 mmol); oxidant (10 mmol); Solvent (10 mL); 50 mg catalyst at 60 0C for 8
hr. aYield refers to GC & GC-MS analysis. b5 mmol 30% H2O2 was used. c10 mmol 30% H2O2
was used. d20 mmol 30% H2O2 was used.
4
Table S3. Oxidation of benzylalcohol using different solvents catalyzed by polymer supported
iron Schiff base complex.
Run
Solvent
Oxidant
Yield of PhCHO (%)a
1
MeOH
H2O2
75
2
EtOH
H2O2
71
BuOH
H2O2
63
4
DMF
H2O2
81
5b
CH3CN
H2O2
94
5
DMSO
H2O2
83
6
Acetone
H2O2
78
7
AcOH
H2O2
96
8c
CH3CN
H2O2
94
9d
CH3CN
H2O2
92
10e
CH3CN
H2O2
59
3
t
Conditions: Benzyl alcohol (5 mmol); oxidant (10 mmol); Solvent (10 mL); 50 mg catalyst at
room temparature for 8 hr. aYield refers to GC & GC-MS analysis. bReaction temperature 60 0C.
c
Reaction temperature 50 0C. dRoom temperature. e20 mmol 30% H2O2 was used.
5
Table S4. Oxidation of thioanisole using different solvents catalyzed by polymer-anchored iron
Schiff base complex.
Yeild of sulfoxide (%)a,b
Run
Solvent
1
CH2Cl2
H2O2
27
2
AcOEt
H2O2
59
3
Toluene
H2O2
17
4c
CH3CN
H2O2
92
5
CH3CH2CN
H2O2
78
6
MeOH
H2O2
83
7
EtOH
H2O2
82
8
i
PrOH
H2O2
73
9
t
BuOH
H2O2
69
CH3CN
H2O2
91
10d
Oxidant
Conditions: diphenyl sulfide (5 mmol); 30% aq H2O2 (10 mmol); Solvent (10 mL); 50 mg
catalyst at room temperature. aConversion and selectivity were determined by GC. bProducts
were characterized by GC–MS. cReaction temperature was 60 0C. dReaction temperature was 50
0
C. eRoom temperature. f20 mmol 30% H2O2 was used.
6
Table S5. Recyclability test of the catalyst
Catalytic runs →
Run 1
Run 2
Run 3
Run 4
Run 5
Styrene oxidation
91
90
87
84
82
Benzyl alcohol oxidation
92
92
90
86
84
↓Reactions
Table S6. Antibacterial activities of iron(III)-ferrocene Schiff base complex* .
Compound
E.coli (mm)
1000 ppm
Iron(III)chloride
2000 ppm
nil
nil
B.subtilis (mm)
3000 ppm
26.6±0.26
1000 ppm
nil
2000 ppm
3000 ppm
nil
28.0±0.4
ligand
16.3±3.5
20.3±3.0
-
18.3±2.0
21.7±1.7
-
Iron(III)ferrocene
complex
20.5±2.6
24.5±2.5
-
22.5±3.2
25.7±1.4
-
Streptomycin
13.5±2.3
15.5±2.2
-
12.9±3.0
15.4±2.4
-
*Inhibition zone diameter in mm.
7
Spectral data of the products
OH
1-adamantanol [1]: 1H NMR (CDCl3) δ (ppm) 4.12 (s, 1H), 2.11-2.16 (m, 3H) 1.90-1.96 (m,
6H), 1.75-1.79 (m, 6H); 13C NMR (CDCl3) δ (ppm) 67.7, 45.6, 37.0, 32.0.
CHO
Benzaldehyde [2]: 1H NMR (CDCl3) δ (ppm) 10.15 (s, 1H), 7.90 (d, 2H), 7.65 (m, 1H), 7.52 (m,
2H); 13C NMR (CDCl3) δ (ppm) 192.4, 136.0, 134.0, 130.3, 129.6.
CHO
O2N
4-Nitrobenzaldehyde [3]: 1H NMR (CDCl3) δ (ppm) 10.17 (s, 1H), 8.40 (d, 2H), 8.09 (d, 2H);
C NMR (CDCl3) δ (ppm) 192.5, 154.0, 143.8, 130.2, 124.3.
13
CHO
Cl
4-Chlorobenzaldehyde [2]: 1H NMR (CDCl3) δ (ppm) 10.16 (s, 1H), 7.82 (d, 2H), 7.60 (d, 2H);
C NMR (CDCl3) δ (ppm) 191.2, 141.0, 134.7, 131.3, 129.8.
13
O
Acetophenone [4]: 1H NMR (CDCl3) δ (ppm) 7.90 (m, 2H), 7.54 (m, 1H), 7.47 (m, 2H), 2.58 (s,
3H); 13C NMR (CDCl3) δ (ppm) 198.0, 137.6, 133.4, 128.7, 128.4, 26.7.
8
O
Propiophenone [5]: 1H NMR (CDCl3) δ (ppm) 7.97 (d, 2H), 7.60 (m, 1H), 7.54 (m, 2H), 3.08 (m,
2H), 1.23 (t, 3H);
13
C NMR (CDCl3) δ (ppm) 200.6, 137.0, 133.3, 129.0, 128.5 128.0, 127.6,
31.9, 8.11.
O
Cl
4-Chloroacetophenone [4]: 1H NMR (CDCl3) δ (ppm) 7.87 (d, 2H), 7.40 (d, 2H), 2.60 (s, 3H);
C NMR (CDCl3) δ (ppm) 196.8, 139.3, 135.7, 129.6, 128.5, 26.8.
13
MeO
O
4-Methoxyacetophenone [4]: 1H NMR (CDCl3) δ (ppm) 7.98 (d, 2H), 6.92 (d, 2H), 3.87 (s, 3H),
2.58 (s, 3H); 13C NMR (CDCl3) δ (ppm) 196.4, 159.9, 130.1, 129.5, 113.5, 55.8, 25.9.
O
4-Methylacetophenone [4]: 1H NMR (CDCl3) δ (ppm)
7.88 (d, 2H),7.26 (d, 2H), 2.55 (s, 3H),
2.39 (s, 3H); 13C NMR (CDCl3) δ (ppm) 197.9, 139.9, 134.7, 129.4, 128.6, 26.2, 21.7.
O
Benzophenone [5]: 1H NMR (CDCl3) δ (ppm) 7.86 (d, 4H), 7.70 (m, 2H), 7.54 (m, 4H); 13C
NMR (CDCl3) δ (ppm) 196.9, 138.0, 132.2, 129.9, 128.0.
9
O
2-Octanone [4]: 1H NMR (CDCl3) δ (ppm) 2.32 (t, 2H), 2.10 (s, 3H), 1.55 (m, 2H), 1.24 (m,
6H), 0.87(q, 3H); 13C NMR (CDCl3) δ (ppm)
209.0, 43.8, 31.7, 29.9, 28.5, 23.8, 22.6, 14.5.
O
Cyclohexanone [5]: 1H NMR (CDCl3) δ (ppm) 2.30 (t, 4H), 1.84 (m, 4H), 1.69 (m, 2H); 13C
NMR (CDCl3) δ (ppm) 211.4, 42.0, 26.9, 25.1
Br
O
4-Bromobenzaldehyde [2]: 1H NMR (CDCl3) δ (ppm) 9.7 (s, 1H), 7.70-7.81 (m, 4H); 13C NMR
(CDCl3) δ (ppm) 192.1, 135.6, 132.0, 130.9, 129.1
O
Verbenone [6]: 1H NMR (CDCl3) δ (ppm) 5.65 (brs, 1H), 2.79 (t, 1H), 2.66 (t, 1H), 2.43 (d, 1H),
2.10 (d, 1H), 2.04 (d, 3H), 1.53 (s, 3H), 1.05 (s, 3H); 13C NMR (CDCl3) δ (ppm) 204.1, 169.2,
121.0, 57.8, 53.7, 49.8, 40.6, 26.5, 23.6, 22.3
O
Carvone [7]: 1H NMR (CDCl3) δ (ppm) 6.73 (m, 1H), 4.67-4.79 (s, 2H) 2.80–2.30 (m, 5H), 1.73
(s, 6H); 13C NMR (CDCl3) δ (ppm), 200.1, 147.2, 145.0, 135.7, 110.8, 43.5, 42.4, 31.6, 20.6, ,
16.1.
10
O
MeO
2-Methoxybenzaldehyde [2]: 1H NMR (CDCl3) δ (ppm) 9.99 (s, 1H), 7.59 (d, 1H), 7.54 (m, 1H),
7.29 (m, 1H), 7.12 (d, 1H), 3.80 (s, 3H); 13C NMR (CDCl3) δ (ppm) 191.9, 164.0, 136.4, 131.5,
125.1, 121.3, 112.0, 55.2
Cl
OHC
2-Chlorobenzaldehyde [2]: 1H NMR (CDCl3) δ (ppm) 10.39 (s, 1H), 7.90 (d, 1H), 7.42-7.57 (m,
3H); 13C NMR (CDCl3) δ (ppm) 189.4, 137.3, 135.6, 133.9, 131.4, 131.0, 127.3
O
O
Benzil [8]: 1H NMR (CDCl3) δ (ppm) 7.95 (d, 4H,), 7.68-7.71 (m, 2H), 7.49-7.54 (m, 4H); 13C
NMR (CDCl3) δ (ppm) 194.7, 134.6, 132.9, 130.1, 128.9
O
Acetone [9]: 1H NMR (CDCl3) δ (ppm) 2.17 (s, 6H); 13C NMR (CDCl3) δ (ppm) 206.9, 31.0
O
2,2-Dimethylpropiophenone [5]: 1H NMR (CDCl3) δ (ppm) 7.59 (d, 2H), 7.19-7.49 (m, 3H),
1.28 (s, 9H); 13C NMR (CDCl3) δ (ppm) 209.9, 138.5, 131.0, 127.3, 127.6, 44.7, 28.4
11
O
S
Diphenyl sulfoxide [10]: 1H NMR (CDCl3) δ (ppm) 7.59-7.65 (m, 4H), 7.39-7.45 (m, 6H); 13C
NMR (CDCl3) δ (ppm), 145.8, 131.4, 129.0, 124.3
O
S
Cyclohexylphenyl sulfoxide [11]: 1H NMR (CDCl3) δ (ppm) 7.53-7.59 (m, 2H), 7.42-7.51 (m,
3H), 2.79 (t, 2H), 1.68-1.75 (m, 1H), 1.52-1.59 (m, 1H), 1.29-1.41 (m, 2H), 1.21-1.26 (m, 4H),
0.90 (t, 3H) ; 13C NMR (CDCl3) δ (ppm) 142.9, 130.4, 129.0, 123.8, 57.0, 31.4, 28.6, 22.5, 21.9,
14.0
O
S
O
Methyl(4-methoxyphenyl) sulfoxide [12]: 1H NMR (CDCl3) δ (ppm)7.60 (d, 2H), 6.99 (d, 2H),
3.81 (s, 3H), 2.70 (s, 3H); 13C NMR (CDCl3) δ (ppm) 162.3, 136.4, 125.3, 114.9, 55.8, 39.9
O
S
Methylphenyl sulfoxide [10]: 1H NMR (CDCl3) δ (ppm) 2.64 (s, 3H), 7.48-7.54 (m, 3H), 7.587.60 (m, 2H); 13C NMR (CDCl3) δ (ppm) 44.0, 123.4, 129.5, 130.9, 145.7
O
S
Ethylphenyl sulfoxide [10]: 1H NMR (CDCl3) δ (ppm) 7.41-7.59 (m, 5H) 2.87-2.92 (m, 1H),
2.68-2.78 (m, 1H), 1.65 (t, 3H) ; 13C NMR (CDCl3) δ (ppm) 143.8, 131.6, 128.9, 124.6, 49.5, 7.1
12
O
S
Phenyl (prop-1-ene) sulfoxide [11]: 1H NMR (CDCl3) δ (ppm) 7.87-7. 90 (m, 2H), 7.59-7.63
(m, 1H), 7.48-7.53 (m, 2H), 5.72-5.81 (m, 1H), 5.29 (d, 1H), 5.14 (d, 1H), 3.78 (d, 2H) ; 13C
NMR (CDCl3) δ (ppm) 138.6, 133.7, 129.5, 128.4, 124.7, 124.1, 60.3
O
S
Benzylphenyl sulfoxide [11]: 1H NMR (CDCl3) δ (ppm) 7.38-7.44 (m, 5H) 7.18-7.24 (m, 3H),
6.91 (d, 2H), 4.10 (d, 1H), 3.99 (d, 1H); 13C NMR (CDCl3) δ (ppm) 143.0, 131.6, 130.3, 129.5,
128.5, 128.2, 127.9, 124.2, 63.5
S
O
Dimethyl sulfoxide [9]: 1H NMR (CDCl3) δ (ppm) 2.58 (s, 6H); 13C NMR (CDCl3) δ (ppm) 40.3
Pr
S
Pr
O
Di(n-propyl) sulfoxide [13]: H NMR (CDCl3) δ (ppm) 2.69–2.75 (m, 2H), 2.54–2.61(m, 2H),
1
1.80 (m, 4H), 1.10 (t, 6H); 13C NMR (CDCl3) δ (ppm) 54.41, 16.11, 13.49
S
13
O
Di(n-butyl) sulfoxide [11]: 1H NMR (CDCl3) δ (ppm) 2.60-2.71 (m, 4H, CH2) 1.68-1.74 (m, 4H,
CH2), 1.41-1.49 (m, 4H, CH2), 0.92 (t, 6H, CH3); 13C NMR (CDCl3) δ (ppm) 51.9, 24.8, 22.5,
13.9
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