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Supplementary material to CuIBiOI is an efficient novel catalyst in Ullmann-type C

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Supplementary material to

Cu

I

BiOI 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)

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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

5/2

I 3d

3/2

A

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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S3

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.

(4)

S4

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

2

O Et OH H

2

O/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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S5

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

(6)

S6

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.

(7)

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

Ábra

Fig. S2. Deconvoluted XP spectra of the A: I 3d and B: O 1s regions for the as-prepared phase- phase-pure Cu I BiOI
Fig. S3. BET isotherms for the Cu I BiOI and the BiOI oxohalides.
Fig.  S5.  Investigating  various  solvents  and  reaction  temperatures  in  the  Cu I BiOI  catalyzed  Ullmann-type  reaction
Fig. S6. Ullmann-type C–N coupling reaction between chlorobenzene and aqueous ammonia

Hivatkozások

KAPCSOLÓDÓ DOKUMENTUMOK

b Materials and Solution Structure Research Group and Interdisciplinary Excellence Centre, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-

d Material and Solution Structure Research Group, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, H-6720 Szeged, Hungary.. e MTA-SZTE Reaction Kinetics

b Department of Physical Chemistry and Material Science, University of Szeged, 1 Rerrich Béla tér, H–6720 Szeged, Hungary.. c Department of Chemistry, Babes-Bolyai University,

Department of Geometry, Bolyai Institute, University of Szeged, Aradi v´ ertan´ uk tere 1, 6720 Szeged, Hungary, and Department of Mathematics and Statistics, Uni- versity of

Department of Geometry, Bolyai Institute, University of Szeged, Aradi v´ ertan´ uk tere 1, H-6720 Szeged, Hungary.. E-mail

Project title: “Broadening the knowledge base and supporting the long term professional sustainability of the Research University Centre of Excellence at the University of Szeged

Project title: “Broadening the knowledge base and supporting the long term professional sustainability of the Research University Centre of Excellence at the University of Szeged

Project title: “Broadening the knowledge base and supporting the long term professional sustainability of the Research University Centre of Excellence at the University of Szeged