Supplementary File

A Thiosemicarbazone-palladium(II)-imidazole complex as an efficient pre-catalyst for Suzuki-Miyaura cross-coupling reactions at room temperature in

aqueous media

Jayantajit Baruaha , Rajjyoti Gogoia , Nibedita Gogoi a & Geetika Boraha, * aDepartment of Chemistry, Dibrugarh University, Dibrugarh ,Assam, India

email: jayantajit09@gmail.com, geetikachem@yahoo.co.in

Fig. S1: 1H-NMR of [PdL1Cl2]

Fig. S2: 13C-NMR of [PdL1Cl2]

Fig. S3: 1H-NMR of C1

Fig. S4: 13C-NMR of C1

Fig: S5: TEM image of C1 after first catalytic cycle (SAED, in the

inset)

Fig. S6: SEM-EDX spectrum of C1 after first

catalytic cycle

Fig. S7: XRD pattern of C1 after the first catalytic cycle

Fig.S8: TEM image of C1 after the sixth catalytic cycle

1H-NMR spectra for all the isolated products

Product no 1, 11, 18, 20: (4-methoxy-1,1'-biphenyl):

(CDCl3, 300MHz, ppm) 7.599-7.213 (m, 6H, Ph), 6.989-6.932 (m, 2H, Ph), 3.852(s, 3H, CH3)

Product no 2, 21, 22: (4-nitro-1,1'-biphenyl): (CDCl3, 300MHz, ppm):

8.336-8.636 (d, 2H, Ph), 8.102-8.076 (d, 1H, Ph), 7.801-7.718 (m, 2H, Ph), 7.438-7.421(m, 4H,

Ph)

Product no 3: ([1,1'-biphenyl]-4-carbaldehyde):

(CDCl3, 300MHz, ppm) 10.088-10.010 (m, 1H, CH), 7.990-7.251 (m, 8H, Ph)

Product no 4:(4'-methyl-3-nitro-1,1'-biphenyl):

(CDCl3, 300MHz, ppm)8.462-8.436 (d, 1H, Ph), 8.220-7.710 (m, 5H, Ph), 7.341-7.318 (d, 2H,

Ph), 2.755(s, 3H, CH3).

Product no 5: (4'-methoxy-[1,1'-biphenyl]-4-carbaldehyde):

(CDCl3, 300MHz, ppm) 10.073-10.008 (m, 1H, CH), 7.979-7.380 (m, 8H, Ph), 3.812-3.877(s,

3H, CH3)

Product no 6: ([1,1'-biphenyl]-3-carbaldehyde):

(CDCl3, 300MHz, ppm) 9.985-9.945 (t, 1H, CH), 8.065-6.856 (m, 9H, Ph)

Product no 7: ([1,1'-biphenyl]-2-carbaldehyde):

(CDCl3, 300MHz, ppm) 10.016-9.985 (t, 1H, CH), 8.065-7.219 (m, 9H, Ph)

Product no 8: ([1,1'-biphenyl]-4-carbonitrile):

(CDCl3, 300MHz, ppm) 7.762-7.256 (m, 9H, Ph)

Product no 9, 19: (4,4'-dimethoxy-1,1'-biphenyl):

(CDCl3, 300MHz, ppm) 7.668-7.642 (d, 4H, Ph), 6.996-6.779 (m, 4H, Ph), 3.833(s, 6H, CH3)

Product no 10: (4'-methoxy-3-nitro-1,1'-biphenyl):

(CDCl3, 300MHz, ppm) 8.462-8.436 (d, 1H, Ph), 8.220-8.167 (d, 3H, Ph), 7.966-7.540 (m, 2H,

Ph), 7.121-7.048 (m,2H, Ph), 3.828(s, 3H,CH3)

Product no 12: (4-methoxy-4'-nitro-1,1'-biphenyl):

(CDCl3, 300MHz, ppm) 8.362-8.345 (d, 2H, Ph), 7.924-7.866 (m, 2H, Ph), 7.692-7.542 (m,

2H, Ph), 7.120-7.045 (m, 2H, Ph), 3.825(s, 3H, CH3)

Product no 13: (3-methoxy-1,1'-biphenyl):

(CDCl3, 300MHz, ppm) 7.633-6.865 (m, 9H, Ph), 3.858-3.818 (s, 3H, CH3)

Product no 14: (1-([1,1'-biphenyl]-4-yl)ethanone):

(CDCl3, 300MHz, ppm) 8.091-8.011(m, 2H, Ph), 7.744-7.224(m,7H, Ph), 2.690-2.610 (s, 3H,

CH3)

Product no 15: (3-(4-methoxyphenyl)thiophene):

(CDCl3, 300MHz, ppm) 7.978-7.518 (m, 4H, Ph), 7.286-7.120(m, 3H, Ph), 3.831(s, 3H, CH3)

Product no 16: (4'-fluoro-3-nitro-1,1'-biphenyl):

(CDCl3, 300MHz, ppm): 8.642-8.636 (d, 1H, Ph), 8.167-8.096 (d, 1H, Ph), 7.787-7.694 (m,

2H,Ph), 7.456-7.318 (m, 4H, Ph)

Product no 17: (1-(4'-nitro-[1,1'-biphenyl]-4-yl)ethanone):

(CDCl3, 300MHz, ppm) 8.361-8.080 (m, 4H, Ph), 7.806-7.720 (m, 4H, Ph), 2.675(s, 3H, CH3)

Table S1: Crystal data and structure refinement for [PdL1L2Cl] ,C1 complex

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[PdL1L2Cl] ,C1

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Empirical formula C19 H20 Cl N5 O Pd S

Formula weight 508.31

Temperature 293(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 20.8151(15) Å a= 90°.

b = 8.3529(7) Å b= 103.490(3)°.

c = 12.5068(10) Å g = 90°.

Volume 2114.5(3) Å3

Z 4

Density (calculated) 1.597 Mg/m3

Absorption coefficient 1.122 mm-1

F(000) 1024

Crystal size 0.300 x 0.200 x 0.200 mm3

Theta range for data collection 2.012 to 26.000°.

Index ranges -25<=h<=25, -10<=k<=10, -15<=l<=15

Reflections collected 28596

Independent reflections 4157 [R(int) = 0.0429]

Completeness to theta = 25.242° 99.7 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.78 and 0.65

Data / restraints / parameters 4157 / 56 / 279

Goodness-of-fit on F2 1.143

Final R indices [I>2sigma(I)] R1 = 0.0524, wR2 = 0.1148

R indices (all data) R1 = 0.0733, wR2 = 0.1381

Largest diff. peak and hole 1.416 and -0.691 e.Å-3

Table S2: Selected bond lengths [Å] and angles [°] for complex C1

Bond lengths Bond lengthsC(1)-N(2) 1.287(8) C(12)-O(1) 1.385(13)C(1)-N(3) 1.353(8) C(12)-C(13) 1.373(10)C(1)-S(1) 1.746(6) C(13)-C(14) 1.376(9)C(2)-C(3) 1.369(9) C(15)-C(16) 1.344(10)C(2)-C(7) 1.370(9) C(15)-N(4) 1.364(9)C(2)-N(3) 1.411(8) C(16)-N(5) 1.345(9)C(3)-C(4) 1.368(10) N(5)-C(17) 1.323(8)C(4)-C(5) 1.378(12) N(5)-C(18) 1.471(9)C(5)-C(6) 1.349(12) C(17)-N(4) 1.315(8)C(6)-C(7) 1.377(10) N(1)-N(2) 1.393(7)C(8)-N(1) 1.285(7) N(1)-Pd(1) 2.015(5)C(8)-C(9) 1.450(8) N(4)-Pd(1) 2.019(5)C(9)-C(10) 1.385(9) C(19)-O(1) 1.440(15)C(9)-C(14) 1.387(9) O(1')-C(19') 1.427(13)C(10)-C(11) 1.366(9) S(1)-Pd(1) 2.2260(18)C(11)-C(12) 1.372(10) Cl(1)-Pd(1) 2.3407(17)Bond angles Bond angles

N(2)-C(1)-N(3) 121.0(6) C(1)-N(3)-C(2) 130.4(6)N(2)-C(1)-S(1) 124.8(5) C(17)-N(4)-Pd(1) 127.5(5)N(3)-C(1)-S(1) 114.2(5) C(15)-N(4)-Pd(1) 126.7(5)N(1)-C(8)-C(9) 131.2(6) C(1)-S(1)-Pd(1) 96.8(2)N(1)-C(8)-H(8) 114.4 N(1)-Pd(1)-N(4) 174.7(2)C(9)-C(8)-H(8) 114.4 N(1)-Pd(1)-S(1) 84.11(15)C(8)-N(1)-N(2) 116.1(5) N(4)-Pd(1)-S(1) 91.21(15)C(8)-N(1)-Pd(1) 123.1(4) N(1)-Pd(1)-Cl(1) 97.18(14)N(2)-N(1)-Pd(1) 120.6(4) N(4)-Pd(1)-Cl(1) 87.72(15)C(1)-N(2)-N(1) 113.6(5) S(1)-Pd(1)-Cl(1) 174.17(8)

Table S3: Turn over number (TON) and turn over frequency (TOF) of C1 from first to seventh

catalytic cycles

Cycle No 1st 2nd 3rd 4th 5th 6th 7th

TON 66 81 79 76 76 75 74

TOF (h-1) 11 81 53 51 38 37 25

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