Supporting Information

Thiazole-based non-symmetric NNC-Palladium pincer complexes as catalytic precursors for the Suzuki–Miyaura C-C coupling

Martín Camacho-Espinoza, Alberto Reyes-Deloso, R. Alfredo Toscano, J. Guillermo Penieres-Carrillo, José G. López-Cortés, M. Carmen Ortega-Alfaro, and Fernando Ortega-Jiménez.

CONTENTS

i. FT-IR, MS and NMR spectra of ligand 1a-c S1

ii. FT-IR, MS and NMR spectra of palladadium complexes 2a-c S19

iii. Spectroscopic data of coupling products S37

iii. NMR spectra of coupling products S40

iii. References S60

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019

S1

FT-IR compound 1a

MS-DART compound 1a

N

S NN

N

S NN

S2

1H NMR (300 MHz, CDCl3) compound 1a

13C NMR (75 MHz, CDCl3) compound 1a

N

S NN

N

S NN

S3

FT-IR compound 1b

MS-DART compound 1b

N

S NN

N

S NN

S4

1H NMR (300 MHz, CDCl3) compound 1b

13C NMR (75 MHz, CDCl3) compound 1b

N

S NN

N

S NN

S5

FT-IR compound 1c

MS-DART compound 1c

N

S NN

Ph

N

S NN

Ph

S6

1H NMR (300 MHz, CDCl3) compound 1c

13C NMR (75 MHz, CDCl3) compound 1c

N

S NN

Ph

N

S NN

Ph

S7

FT-IR compound 1d

MS-DART compound 1d

N

S NN

N

S NN

S8

1H NMR (300 MHz, CDCl3) compound 1d

13C NMR (75 MHz, CDCl3) compound 1d

N

S NN

N

S NN

S9

FT-IR compound 1e

MS-EI compound 1e

N

S NN

N

S NN

S10

1H NMR (300 MHz, CDCl3) compound 1e

13C NMR (75 MHz, CDCl3) compound 1e

N

S NN

N

S NN

S11

FT-IR compound 1f

MS-DART compound 1f

N

S NN

Ph

N

S NN

Ph

S12

1H NMR (300 MHz, CDCl3) compound 1f

13C NMR (75 MHz, CDCl3) compound 1f

N

S NN

Ph

N

S NN

Ph

S13

FT-IR compound 1g

MS-EI compound 1g

N

S NN

H3C

N

S NN

H3C

S14

1H NMR (300 MHz, CDCl3) compound 1g

13C NMR (75 MHz, CDCl3) compound 1g

N

S NN

H3C

N

S NN

H3C

S15

FT-IR compound 1h

MS-DART compound 1h

N

S NN

H3C

CH3

N

S NN

H3C

CH3

S16

1H NMR (300 MHz, CDCl3) compound 1h

13C NMR (75 MHz, CDCl3) compound 1h

N

S NN

H3C

CH3

N

S NN

H3C

CH3

N

S NN

H3C

CH3

S17

FT-IR compound 1i

MS-DART compound 1i

N

S NN

H3C

N

S NN

H3C

S18

1H NMR (300 MHz, CDCl3) compound 1i

13C NMR (75 MHz, CDCl3) compound 1i

N

S NN

H3C

N

S NN

H3C

S19

FT-IR compound 2a

MS-FAB+ compound 2a

N

S NN

PdCl

N

S NN

PdCl

S20

1H NMR (500 MHz, CD2Cl2) compound 2a

13C NMR (125 MHz, CD2Cl2) compound 2a

N

S NN

PdCl

N

S NN

PdCl

S21

FT-IR compound 2b

MS-FAB+ compound 2b

N

S NN

PdCl

N

S NN

PdCl

S22

1H NMR (300 MHz, DMSO-d6) compound 2b

13C NMR (75 MHz, DMSO-d6) compound 2b

N

S NN

PdCl

N

S NN

PdCl

S23

FT-IR compound 2c

MS-FAB+ compound 2c

N

S NN

PdCl

Ph

N

S NN

PdCl

Ph

S24

1H NMR (500 MHz, CD2Cl2) compound 2c

13C NMR (125 MHz, CD2Cl2) compound 2c

N

S NN

PdCl

Ph

N

S NN

PdCl

Ph

S25

FT-IR compound 2d

MS-FAB+ compound 2d

N

S NN

PdCl

N

S NN

PdCl

S26

1H NMR (500 MHz, CD2Cl2) compound 2d

13C NMR (125 MHz, CD2Cl2) compound 2d

N

S NN

PdCl

N

S NN

PdCl

S27

FT-IR compound 2e

MS-FAB+ compound 2e

N

S NN

PdCl

N

S NN

PdCl

S28

1H NMR (300 MHz, DMSO-d6) compound 2e

13C NMR (75 MHz, DMSO-d6) compound 2e

N

S NN

PdCl

N

S NN

PdCl

S29

FT-IR compound 2f

MS-FAB+ compound 2f

N

S NN

PdCl

Ph

N

S NN

PdCl

Ph

S30

1H NMR (500 MHz, CD2Cl2) compound 2f

13C NMR (125 MHz, CD2Cl2) compound 2f

N

S NN

PdCl

Ph

N

S NN

PdCl

Ph

S31

FT-IR compound 2g

MS-FAB+ compound 2g

N

S NN

H3CPdCl

N

S NN

H3CPdCl

S32

1H NMR (300 MHz, DMSO-d6) compound 2g

13C NMR (75 MHz, DMSO-d6) compound 2g

N

S NN

H3CPdCl

N

S NN

H3CPdCl

S33

FT-IR compound 2h

MS-FAB+ compound 2h

N

S NN

H3C

CH3

PdCl

N

S NN

H3C

CH3

PdCl

S34

1H NMR (300 MHz, DMSO-d6) compound 2h

13C NMR (75 MHz, DMSO-d6) compound 2h

N

S NN

H3C

CH3

PdCl

N

S NN

H3C

CH3

PdCl

S35

FT-IR compound 2i

MS-FAB+ compound 2i

N

S NN

H3CPdCl

N

S NN

H3CPdCl

S36

1H NMR (300 MHz, DMSO-d6) compound 2i

13C NMR (75 MHz, DMSO-d6) compound 2i

N

S NN

H3CPdCl

N

S NN

H3CPdCl

S37

4-Methoxybiphenyl 5a.1 White solid. mp 88-90 °C. 1H-NMR (300 MHz, CDCl3) : 3.85 (s,

3H, OCH3), 6.98 (d, J = 8.0 Hz, 2H, Ar), 7.30 (t, J = 7.6 Hz, 1H, Ar); 7.42 (t, J = 7.5 Hz, 2H,

Ar), 7.50-7.57 (m, 4H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.1, 126.6, 126.7, 128.1,

128.7, 133.7, 140.8, 159.1.

4-Methylbiphenyl 5b.1 White solid. mp 45-47 °C. 1H-NMR (300 MHz, CDCl3) : 2.39 (s,

3H, CH3), 7.26 (d, J = 7.8 Hz, 2H, Ar), 7.31(t, J = 7.8 Hz, 1H, Ar), 7.42 (t, J = 7.8 Hz, 2H,

Ar), 7.50 (d, J = 8.4 Hz, 2H, Ar), 7.59 (d, J = 7.8 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3)

:21.0, 126.9, 128.6, 129.4, 136.9, 138.3, 141.1.

3-Methylbiphenyl 5c.2 Colorless oil. 1H-NMR (300 MHz, CDCl3) : 2.59 (s, 3H, CH3), 7.35

(d, J = 7.5 Hz, 1H, Ar), 7.50 (t, J = 7.5 Hz, 2H, Ar), 7.60 (t, J = 7.5 Hz, 4H, Ar), 7.76 (d, J =

7.5 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 21.4, 124.2, 127.1, 127.9, 128.6, 13802.

141.1, 141.3

2-Methylbiphenyl 5d.1 Colorless oil. 1H-NMR (300 MHz, CDCl3) : 2.58 (s, 3H, CH3), 7.54-

7.68 (m, 9H, Ar),. 13-CNMR (75 MHz, CDCl3) : 20.3, 125.7,126.6, 127.1, 127.9, 129.1,

129.7, 130.2, 135.1, 141.9.

1-phenylnaphthalene 5e.1 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.38 (d, J = 7.2 Hz,

1H, Ar), 7.51-7.46 (m, 4H, Ar), 7.76-7.72 (m, 3H, Ar), 7.93-7.85 (m, 3H, Ar), 8.05 (s, 1H,

Ar). 13-CNMR (75 MHz, CDCl3) : 123.1, 124.7, 125.9, 127.1, 127.4, 127.9, 128.7, 128.8,

132.1, 134.4, 140.0, 142.4.

2,6-dimethylbiphenyl 5f.3 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 2.0 (s, 6H, CH3),

7.11-7.17 (m, 4H, Ar), 7.35 (t, J = 6.6 Hz, 1H, Ar), 7.42 (t, J = 6.6 Hz, 1H, Ar), 7.42 (d, J =

6.6 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 20.8, 126.5, 126.9, 127.1, 127.2, 128.3,

128.7, 129.0, 136.0, 141.0, 141.8.

Biphenyl 5g.1 White solid. mp 68-70°C. 1H-NMR (300 MHz, CDCl3) : 7.34 (t, J = 7.2 Hz,

2H, Ar). 7.44 (t, J = 7.2 Hz, 4H, Ar), 7.61 (d, J = 7.2 Hz, 4H, Ar). 13-CNMR (75 MHz,

CDCl3) : 127.1. 127.2, 128.7, 141.2.

S38

4-Nitrobiphenyl 5h.1 Yellow solid. mp 112-114 °C. 1H-NMR (300 MHz, CDCl3) : 7.44-7.52

(m, 3H, Ar), 7.63 (d, J = 8.1 Hz, 2H, Ar), 7.75 (d, J = 9.3 Hz, 2H, Ar), 8.31 (d, J = 8.4 Hz,

2H, Ar). 13-CNMR (75 MHz, CDCl3) : 124.0, 127.3, 127.7, 128.8, 129.1, 138.7, 147.0,

147.5.

4-Acetylbiphenyl 5i.1 White solid. mp 120-121°C. 1H-NMR (300 MHz, CDCl3) : 2.64 (s,

3H, CH3), 7.40 (d, J = 7.6 Hz, 1H, Ar), 7.47 (t, J = 7.6 Hz, 2H, Ar), 7.62 (d, J = 7.6 Hz, 2H,

Ar), 7.70 (d, J = 8.0 Hz, 2H, Ar), 8.05 (d, J = 8.0 Hz, 2H, Ar). CNMR (75 MHz, CDCl3) :

197.9, 145.7, 139.8, 135.8, 128.9, 128.2, 127.3 127.2, 26.6.

2-phenylpyridine 5j.4 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.32-7.59 (m, 6H, Ar),

7.87 (d, J = 7.2 Hz 1H, Ar), 8.59 (d, J = 6.3 Hz 1H, Ar), 8.85 (d, J = 4.8 Hz, 1H, Ar). 13-

CNMR (75 MHz, CDCl3) : 123.4, 127.0, 128.0, 128.7, 128.9, 130.7, 134.2, 136.5, 137.7,

148.2, 148.3.

3-phenylpyridine 5k.5 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.34-7.37 (m, 3H, Ar),

7.44 (t, J = 7.8 Hz 2H, Ar), 7.58 (d, J = 7.2 Hz 2H, Ar), 8.62 (d, J = 4.8 Hz, 2H, Ar). 13-

CNMR (75 MHz, CDCl3) : 121.2, 127.1, 127.2, 128.7, 141.2, 150.1, 152.1.

2-phenylthiophene 5l.4 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.06-7.09 (m, 1H, Ar),

7.25-7.44 (m, 5H, Ar), 7.60-7.63 (m, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 123.0, 124.7,

125.9, 127.1, 127.4, 127.9, 128.7, 128.8.

3-phenylthiophene 5m.6 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.29-7.47 (m, 6H,

Ar), 7.61 (d, J = 9.6 Hz, 2H, Ar).13-CNMR (75 MHz, CDCl3) : 119.7, 120.2, 126.1, 126.3,

126.4, 127.1, 128.7.

4-methoxy-4'-methylbiphenyl 5n.5 White solid. mp 112-114 °C. 1H-NMR (300 MHz, CDCl3)

: 2.38 (s, 3H, CH3), 3.84 (s, 3H, OCH3), 6.98 (d, J = 8.7 Hz, 2H, Ar), 7.24 (d, J = 7.8 Hz,

2H, Ar), 7.46 (d, J = 7.8 Hz, 2H, Ar), 7.52 (d, J = 8.7 Hz, 2H, Ar). 13-CNMR (75 MHz,

CDCl3) : 21.0, 55.3, 114.1, 126.5, 127.9, 128.7, 129.4, 130.8, 133.7, 136.3, 137.9, 158.8.

4,4'-dimethoxybiphenyl 5o.7 White solid. mp 178-180 °C. 1H-NMR (300 MHz, CDCl3) :

3.84 (s, 6H, OCH3), 6.97 (d, J = 9.0 Hz, 4H, Ar), 7.45 (d, J = 9.0 Hz, 4H, Ar). 13-CNMR (75

MHz, CDCl3) : 55.3, 114.1, 127.7, 133.4, 158.6.

S39

4-methoxy-4'-nitrobiphenyl 5p.5 White solid. mp 106-108 °C. 1H-NMR (300 MHz, CDCl3)

: 3.87 (s, 3H, OCH3), 7.03 (d, J = 9.0 Hz, 2H, Ar), 7.59 (d, J = 9.0 Hz, 2H, Ar), 7.70 (d, J =

8.7 Hz, 2H, Ar), 8.28 (d, J = 9.0 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.5,

124.1, 127.0, 128.5, 131.0, 146.4, 147.1, 160.3.

4-methoxy-4'-(trifluoromethyl)biphenyl 5q.8 White solid. mp 124-126 °C. 1H-NMR (300

MHz, CDCl3) : 3.86 (s, 3H, OCH3), 7.02 (d, J = 9.0 Hz, 2H, Ar), 7.56 (d, J = 9.0 Hz, 2H,

Ar), 7.65 (s, 4H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.4, 122.5, 125.6, 126.1, 126.8,

128.3, 128.8, 130.8, 132.1, 144.2, 159.8.

4-methyl-‘4-nitro-biphenyl 5r.8 White solid. mp 132-134 °C. 1H-NMR (300 MHz, CDCl3) :

2.42 (s, 3H, Me). 7.31 (d, J = 7.8 Hz, 2H, Ar), 7.54 (d, J = 8.4 Hz, 2H, Ar),7.73 (d, J = 9.0

Hz, 2H, Ar) 8.29 (d, J = 9.0 Hz, 2H, Ar), 13-CNMR (75 MHz, CDCl3) : 21.1, 124.0, 127.1,

127.4, 129.8, 135.8, 139.0, 146.8, 147.5.

4-nitro-4'-(trifluoromethyl)biphenyl 5s.9 White solid. mp 108-110 °C. 1H-NMR (300 MHz,

CDCl3) : 7.75-7.78 (m, 6H, Ar), 8.36 (d, J = 8.70 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3)

: 124.3, 126.1, 127.7, 128.1, 128.8, 130.8, 146.0, 147.6.

4,4’-dinitro-4'-biphenyl 5t.9 White solid. mp 240-242 °C. 1H-NMR (300 MHz, CDCl3) :

7.81 (d, J = 9.3 Hz, 4H, Ar), 8.38 (d, J = 9.0 Hz, 4H, Ar). 13-CNMR (75 MHz, CDCl3) :

124.4, 128.3, 144.9, 148.0.

S40

1H NMR (300 MHz, CDCl3) compound 5a

13C NMR (75 MHz, CDCl3) compound 5a

H3CO

H3CO

S41

1H NMR (300 MHz, CDCl3) compound 5b

13C NMR (75 MHz, CDCl3) compound 5b

H3C

H3C

S42

1H NMR (300 MHz, CDCl3) compound 5c

13C NMR (75 MHz, CDCl3) compound 5c

CH3

CH3

S43

1H NMR (300 MHz, CDCl3) compound 5d

13C NMR (75 MHz, CDCl3) compound 5d

H3C

H3C

S44

1H NMR (300 MHz, CDCl3) compound 5e

13C NMR (75 MHz, CDCl3) compound 5e

S45

1H NMR (300 MHz, CDCl3) compound 5f

13C NMR (75 MHz, CDCl3) compound 5f

H3C

CH3

H3C

CH3

S46

1H NMR (300 MHz, CDCl3) compound 5g

13C NMR (75 MHz, CDCl3) compound 5g

S47

1H NMR (300 MHz, CDCl3) compound 5h

13C NMR (75 MHz, CDCl3) compound 5h

O2N

O2N

S48

1H NMR (300 MHz, CDCl3) compound 5i

13C NMR (75 MHz, CDCl3) compound 51

H3C

O

H3C

O

S49

1H NMR (300 MHz, CDCl3) compound 5j

13C NMR (75 MHz, CDCl3) compound 5j

N

N

S50

1H NMR (300 MHz, CDCl3) compound 5k

13C NMR (75 MHz, CDCl3) compound 5k

N

N

S51

1H NMR (300 MHz, CDCl3) compound 5l

13C NMR (75 MHz, CDCl3) compound 5l

S

S

S52

1H NMR (300 MHz, CDCl3) compound 5m

13C NMR (75 MHz, CDCl3) compound 5m

S

S

S53

1H NMR (300 MHz, CDCl3) compound 5n

13C NMR (75 MHz, CDCl3) compound 5n

H3CO

CH3

H3CO

CH3

S54

1H NMR (300 MHz, CDCl3) compound 5o

13C NMR (75 MHz, CDCl3) compound 5o

H3CO

OCH3

H3CO

OCH3

S55

1H NMR (300 MHz, CDCl3) compound 5p

13C NMR (75 MHz, CDCl3) compound 5p

H3CO

NO2

H3CO

NO2

S56

1H NMR (300 MHz, CDCl3) compound 5q

13C NMR (75 MHz, CDCl3) compound 5q

H3CO

CF3

H3CO

CF3

S57

1H NMR (300 MHz, CDCl3) compound 5r

13C NMR (75 MHz, CDCl3) compound 5r

O2N

Me

O2N

Me

S58

1H NMR (300 MHz, CDCl3) compound 5s

13C NMR (75 MHz, CDCl3) compound 5s

O2N

CF3

O2N

CF3

S59

1H NMR (300 MHz, CDCl3) compound 5t

13C NMR (75 MHz, CDCl3) compound 5t

O2N

NO2

O2N

NO2

S60

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