Supplementary material to
Cu
IBiOI is an efficient novel catalyst in Ullmann-type C–N couplings with wide scope – A rare non-photocatalyic application
Gábor Vargaa,b*, Marianna Kocsisa,b, Ákos Kukoveczc, Zoltán Kónyac,d, Igor Djerdje, Pál Siposb,f, István Pálinkóa,b*
aDepartment of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary
bMaterials and Solution Structure Research Group, and Interdisciplinary Excellence Centre, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary
cDepartment of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged, H-6720 Hungary
dMTA-SZTE Reaction Kinetics and Surface Chemistry Research Group, Rerrich Béla tér 1, Szeged, H-6720 Hungary
eDepartment of Chemistry, J. J. Strossmayer University of Osijek, Cara Hadrijana 8/a, Osijek,HR-31000 Croatia
fDepartment of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged, H-6720 Hungary
Corresponding authors: István Pálinkó and Gábor Varga
E-mail addresses: palinko@chem.u-szeged.hu (I. Pálinkó), gabor.varga5@chem.u-szeged.hu (G. Varga)
S2
10 20 30 40
Intensi ty (a .u.)
2q (
o)
+ unknown
(200)
(211)
(002) (310)
(001)
(002)
(102)
(110) (112) (004) (001)
(102) (110) (001)
(102) (110)
+ Cu0.2Bi0.8O0.8I0.96Cl0.04
Cu0.18Bi0.88O0.88I1.06 Cu0.48Bi2.42O4
BiOI
A B C D E
(120)
(200)
a–Bi2O3
Fig. S1. XRD patterns of (A) the as-prepared; (B) the heat-treated (at 550°C for 2 h), (C) the used CuIBiOI catalyst, (D) the as-prepared BiOI and (E) the heat-treated BiOI (at 750°C for 2 h).
605 610 615 620 625 630 635
20000 30000 40000 50000 60000 70000 80000
520 525 530 535 540
18000 20000 22000 24000 26000 28000
Intensity (cps)
Binding energy (eV)
619.75
631.25 I 3d
5/2I 3d
3/2A
Intensity (cps)
Binding energy (eV)
530.53
527.79 533.02 O 1s
B
Fig. S2. Deconvoluted XP spectra of the A: I 3d and B: O 1s regions for the as-prepared phase- pure CuIBiOI.
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0.0 0.2 0.4 0.6 0.8 1.0
0 10 20 30
0.0 0.2 0.4 0.6 0.8 1.0
0 20 40 60 80
Volume (cc/g)
p/p0
Adsorption
Desorption
CuBiOI
65 m
2/g
Volume (cc/g)
p/p0
Adsorption
Desorption
BiOI
45 m
2/g
Fig. S3. BET isotherms for the CuIBiOI and the BiOI oxohalides.
0.00 0.02 0.04 0.06 0.08 0.10
0 10 20 30 40 50 60 70 80 90 100
CuBiOI
CuI+OH–L–proline BiOI
Yiel d (%)
Catalysts loading (mmol)
Fig. S4. Optimization of catalyst loading for Ullmann-type C–N coupling reaction between chlorobenzene and aqueous ammonia. Reaction conditions: 1.0 mmol aqueous ammonia; 0.5 mmol chlorobenzene; 0.5 mmol K3PO4; 3.0 ml DMSO; 0.05 mmol organic additive (hydroxy–
L–proline, if it is necessary); T = 110 °C; t = 24 h.
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Table S1
CuIBiOI catalyzed coupling of chlorobenzene and aqueous ammonia in the presence of various bases.a
Bases Yield (%)
K2CO3 79
K3PO4 100
Cs2CO3 93
pyridine 59
piperidine 54
a1.0 mmol aqueous ammonia; 0.5 mmol chlorobenzene; 0.04 mmol catalyst; 0.5 mmol base; 3.0 ml DMSO;
T = 110 °C; t = 24 h
0 50 100
ac etone THF toluene H
2O Et OH H
2O/EtOH
Yield (%) DM SO
A
RT 50 80 reflux
0 20 40 60 80 100
Yield (%)
Reaction temperature (°C)
B
Fig. S5. Investigating various solvents and reaction temperatures in the CuIBiOI catalyzed Ullmann-type reaction. Reaction conditions: 1.0 mmol aqueous ammonia; 0.5 mmol chlorobenzene; 0.04 mmol catalysts; 0.5 mmol K3PO4; 3.0 ml solvent (H2O/EtOH mixture for Fig. S5.(B)); t = 24 h; reflux temperature (except for DMSO; T = 110 °C).
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0 5 10 15 20 25
0 5 10 15 20 25 30
Conversion %
Reaction time (hours)
BiOI
CuI + OH–L–proline CuBiOI
Fig. S6. Ullmann-type C–N coupling reaction between chlorobenzene and aqueous ammonia.
Reaction conditions: 1.0 mmol of aqueous ammonia; 0.5 mmol of chlorobenzene; 0.04 mmol (0.06 mmol in the homogeneous case) of catalyst; 0.5 mmol of K3PO4; 3.0 ml of DMSO;
0.05 mmol of organic additive (hydroxy–L-proline, if it is necessary); T = 80 °C.
1st use 1st recycle 2nd recycle 3rd recycle 4th recycle 5th recycle 0
10 20 30 40 50 60
70 70% 70% 69% 68% 67%
Yield %
70%
Fig. S7. Recyclability of the as-prepared CuIBiOI material tested in Ullmann-type C–N coupling reaction between chlorobenzene and aqueous ammonia. The optimized conditions: 1.0
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mmol aqueous ammonia; 0.5 mmol chlorobenzene; 0.02 mmol catalysts; 0.5 mmol K3PO4; 3 ml EtOH/water (1:1; v/v%); T = 80 °C; t = 20 h.
Mechanistic proposal
It is reasonable to assume that Cu(I) is the key active centre in the catalytic cycle for the CuIBiOI structure. The bismuth(III) component, as a Lewis acid centre, my accelerate the catalytic cycle through coordinating an ammonia molecule. Possible steps are as follows: step I – oxidative addition of aryl halide over Cu(I); step II – coordination of ammonia to the Bi(III) centre followed by proton abstraction by another ammonia molecule; step III – anionoid migration to the Cu(III) reducing to Cu(II) followed by reductive elimination producing the product and regenerating the Cu(I) centre.
S7
Scheme S1 The schematic representation of the possible reaction mechanism of CuIBiOI catalysed Ullmann-type C–N coupling reaction between aryl halides and ammonia