Supporting Information
Palladium-heterogenized Porous Polyimides Materials as Effective and Recycable Catalysts for reactions in Pure Water
E. Rangel Rangel,a E. M. Maya, a F. Sánchez,b J.G. de la Campa,a and M. Iglesiasc
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2014
1.- CHARACTERIZATION OF PPI-n-MATERIALS
Characterization techniques
Elemental analysis (%C, %N and %H) were determined in a LECO CHNS-932 analyzer. ATR- FTIR spectra were recorded on a PerkinElmer Spectrum One spectrometer and are reported in terms of frequency of absorption (cm−1). 13C solid-state NMR measurement was recorded with a Bruker AV400 WB spectrometer (Larmor frequency of 100 MHz, using 4 mm MAS probes spinning at 10 kHz rate). Thermogravimetric analyses (TGA) were conducted in a TA-Q500 analyzer. The samples were heated under an air stream from 40 to 850oC with a heating rate of 10oC/min. WAXS (wide-angle X-ray scattering) was carried out with a Bruker D8 Advance diffractometer. Data were collected stepwise over the 1º≤2θ≤65º angular region, with steps of 0.5 s/step accumulation time and Vantec detector and CuKα (λ = 1.542 Å) radiation. Specific surface area measurement and porosity analysis were performed using N2 adsorption isotherms (Micromeritic, ASAP 2020 MICROPORE dry Analyzer) using the BET technique for surface area calculation and the BJH method for average pore size and pore volume calculations. Prior to measurement, the samples were degassed for 12 h at 100 ºC. Palladium contents were analyzed by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) on a PerkinElmer OPTIMA 2100 DV. Scanning electron microscopy (SEM) micrographs were obtained with a Hitachi SU-8000 microscope operating at 0.5 kV. The samples were prepared directly by dispersing the powder onto a double-sided adhesive surface. The reaction was monitored by gas chromatography on an HP5890 II GC-MS chromatograph, cross-linked methyl silicone column (SPB): 25 m x 0.2 mm x 0.33 mm.
Fig. S1a. Thermograms in air atmosphere of (a) PPI-1, PPI-1-NO2 and PPI-1-NH2; (b) PPI-2, PPI-2-NO2 and PPI-2-NH2
200 400 600 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (ºC)
PPI-2 PPI-2-NO2 PPI-2-NH2
400 6000.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
Der
iv. W
eigh
t (%
/ºC)
Temperature (ºC)
200 400 600 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (ºC)
PPI-1 PPI-1-NO2 PPI-1-NH2
400 6000
1
2
3
4
5
6
7
8
Der
iv. W
eigh
t (%
/ºC)
Temperature (ºC)
Fig. S1b. Thermograms in nitrogen atmosphere of (a) PPI-1, PPI-1-NO2 and PPI-1-NH2; (b) PPI-2, PPI-2-NO2 and PPI-2-NH2
100 200 300 400 500 600 700 80050
60
70
80
90
100
Wei
ght (
%)
Temperature (ºC)
PPI-1 PPI-1-NO2 PPI-1-NH2
300 400 500 600 700 8000.0
0.2
0.4
0.6
0.8
Der
iv. W
eigh
t (%
/ºC)
Temperature (ºC)
NO2
100 200 300 400 500 600 700 80030
40
50
60
70
80
90
100
Wei
ght (
%)
Temperature (ºC)
PPI-2 PPI-2-NO2 PPI-2-NH2
300 400 500 600 700 8000.0
0.2
0.4
0.6
0.8
Der
iv. W
eigh
t (%
/ºC)
Temperature (ºC)
NO2
Fig. S2 Nitrogen sorption isotherm of PPI-1, PPI-2, PPI-1-NH2 and PPI-2-NH2.
Fig. S3 Pore-size distribution of PPI-1, PPI-2, PPI-1-NH2 and PPI-2-NH2.
20 30 40 500.0
0.1
0.2
0.3
0.4
0.5
0.6
dV(R
)/ cm
3 g-1
Å-1
half pore width R/ Å
PPI-1 PPI-2 PPI-1-NH2 PPI-2-NH2
0,0 0,2 0,4 0,6 0,8 1,0
50
100
150
200
250
300
350V N
2 /c
m3 g
-1 S
TP
Relative Pressure p/po
PPI-1 PPI-2 PPI-1-NH2 PPI-2-NH2
Fig. S4 Scanning electron micrographs (SEM) of PPI-1, PPI-1-NO2, PPI-2 and PPI-2-NO2
Fig. S5. TGA and DTG (Vertically shifted) of (a) PPI-1-NH2, PPI-1-NPy and PPI-1-NPy-Pd (b) PPI-2-NH2, PPI-2-NPy and PPI-2-NPy-Pd.
100 200 300 400 500 600 700 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (ºC)
PPI-1-NH2 PPI-1-NPy PPI-1-NPy-Pd
300 400 500 6000
1
2
3
4
5
6
D
eriv
. Wei
ght (
%/ºC
)
Temperature (ºC)
100 200 300 400 500 600 700 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (ºC)
PPI-2-NH2 PPI-2-NPy PPI-2-NPy-Pd
300 400 500 6000
1
2
3
4
5
6
Der
iv. W
eigh
t (%
/ºC)
Temperature (ºC)
Fig. S6 13C-NMR solid spectra of PPI-2-NH2, PPI-2-NPy and PPI-2-NPy-Pd.
Table S1. Elemental analysis of starting, amino-functionalized porous polyimides
% Calculated % Experimental
Polyimide C H N C H N
PPI-1-NH2 71.15 2.77 9.22 55.49 3.66 6.03
PPI-1-NPy 72.17 2.83 9.91 58.80 3.67 6.66
PPI-1-NPy-Pd 59.69 2.34 8.19 55.77 3.29 6.25
PPI-2-NH2 73.24 2.97 8.76 56.76 3.73 6.25
PPI-2-NPy 74.17 3.02 9.61 60.78 3.54 6.99
PPI-2-NPy-Pd 66.14 2.69 8.57 55.25 3.43 6.42
0102030405060708090100110120130140150160170180190200f1 (ppm)
1
2
3
C3v_PDMA_PdCl2.2.fid
C3v_PDMA_NPy.2.fid
emC3VPMDAc.1.fid
165,9 141,7
137,5
126,9
PPI-2
PPI-2-NPy
PPI-2-NPy-Pd
-NH2
Fig. S7. 1H-NMR spectra of NPy and NPy-Pd
Fig. S8. 13C-NMR spectra of NPy and NPy-Pd
o
o
j
j
l
lm
m
n
na, b, c, g, h
N N
abc
de
g hi
j kl m
no
f
N N
PdCl Cl
abc
de
fg h
ij k
l mn
o
jk
oi
d
fm
c b
l
nlh
e
j k o i
d
f m
g
g
c b
a
n
a
he
N N
abc
de
g hi
j kl m
no
f
N N
PdCl Cl
abc
de
g hi
j kl m
no
f
Fig. S9. FT-IR spectra of NPy and NPy-Pd
4000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1)
NPy
NPy-Pd
1632
1595
2.- CATALYTIC STUDIES
Optimization of reaction conditions
Table S2. Suzuki coupling reactions of iodobenzene with phenylboronic acid catalyzed by PPI-1-NPy-Pd.
Cat. mol. (%)b Solvent Base T (ºC) t (h) Yield (%)c TOF (h-1)d 1 1.4 Xylene K2CO3 130 48 14 - 2 1.4 H2O No base 90 48 2 - 3 1.4 H2O K2CO3 90 24 92 5.8 4 1.2 H2O NEt3 100 1 86 72 5 1.2 H2O (i-Pr)2NH 100 1 93 77 6 0.5 H2O (i-Pr)2NH 100 1 73 134 7 0.3 H2O (i-Pr)2NH 100 3 88 462 8 No catalyst H2O (i-Pr)2NH 100 24 - -
aReaction conditions: iodobenzene (1.0 mmol), phenylboronic acid (1.5 mmol), base (2.0 mmol), solvent (1 ml). bBased on Pd; cYield determined by GC and GCMS analysis; dmmol subs./mmol cat. h
Table S3. Suzuki coupling reactions of bromobenzene with various arylboronic acids catalyzed by PPI-1-NPy-Pd and NPy-Pd using water as solvent, DIPA as base at 100 ºC.
X R Catalysts % mol Pd T (h) Conv. (%) Br OMe PPI-1-NPy-Pd 0.5 1
2 3
27 75 93
Br COH PPI-1-NPy-Pd 0.4 0.5 1
1.5
14 43 85
Br CN PPI-1-NPy-Pd 0.8 3 4 5
2 48 93
Br OMe NPy-Pd 0.5 0.5 1 2 3
22 32 35 43
Br COH NPy-Pd 0.4 0.5 1
1.5 2
5 43 48 49
Br CN NPy-Pd 0.8 3 4 5
2.5 4 4
Fig. S10. Kinetic profiles for the PPI-1-NPy-Pd-catalyzed Suzuki reactions between
bromobenzene and arylboronic acids (0.4-0.8 mol% Pd).
0 1 2 3 4 50
10
20
30
40
50
60
70
80
90
100
t [h]
Con
vers
ion
[%]
OMe (cat. 0.5 mol%) NO2 (cat. 0.4 mol%) Me (cat. 0.4 mol%) CHO (cat. 0.4 mol%) CN (cat. 0.8 mol%)
Fig. S11. Kinetic profile for the PPI-2-NPy-Pd-catalyzed Suzuki reactions between
bromobenzene and arylboronic acids (0.5 mol% Pd).
0 1 2 3 4 5 6 70
20
40
60
80
100
Con
vers
ion
[%]
t [h]
OMe NO2 Me CHO CN
Catalyst recyclability experiments: For the recyclability experiment, after each catalytic experiment, the catalyst from the reaction pot was isolated by filtration, washed thoroughly and used for the next cycle of experiment under same reaction condition. Table S4. Recyclability of PPI-1-NPy-Pd for Suzuki coupling reaction
Entry Run Conv. (%) (5 h) TON (5 h) TOF (h-1) 1 1 100 200 150 2 2 98 196 75 3 3 89 178 62 4 4 86 172 58 5 5 86 172 56 6 6 85 170 54 7 7 83 166 53
TON = mmol substrate/mmol cat. TOF= mmol subst/mmol cat. h
Fig. S12. Recycling experiments for Suzuki reaction between bromobenzene and 4-methoxyphenylboronic acid.
1 2 3 40
20
40
60
80
100
Con
vers
ion
[%]
Run
Table S5. Recyclability of PPI-2-NPy-Pd for Suzuki coupling reaction between bromobenzene and 4-methoxyphenylboronic acid.
Entry Run Conv. (%) (5 h) TON TOF (h-1) 1 1 100 200 200 2 2 62 118 26 3 3 42 64 9 4 4 48 86 15 TON = mmol substrate/mmol cat. TOF= mmol subst/mmol cat. h.
Fig. S13. FT-IR spectra of PPI-n-NPy-Pd catalysts before and after recycling.
Fig. S14. WAXS difractograms of PPI-n-NPy-Pd catalysts before and after recycling.
4000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1)
PPI-1-NPy-Pd
PPI-2-NPy-Pd
PPI-2-NPy-Pd-recycled
PPI-1-NPy-Pd-recycled
10 20 30 40 50 60
I (a.
u)
2 (º)
10 20 30 40 50 60
I (a.
u)
2 (º)
PPI-1-NPy-Pd
PPI-1-NPy-Pd-recycled
PPI-2-NPy-Pd
PPI-2-NPy-Pd-recycled
