Electronic Supporting Information For. Accessing Heterobiaryls through Transition Metal-Free C-H Functionalization. Content

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1 Electronic Supporting Information For Accessing Heterobiaryls through Transition Metal-Free C-H Functionalization Ananya Banik, Rupankar Paira*,, Bikash Kumar Shaw, Gonela Vijaykumar and Swadhin K. Mandal*, Department of Chemical Sciences, Indian Institute of Science Education and Research, Kolkata, Mohanpur , India. Department of Chemistry, Maharaja Manindra Chandra College, 20 Ramkanto Bose Street, Kolkata , India. Content ORTEP diagram of ligand 1 S2 Crystal data.. S3-S5 Synthesis of K-coordinated complex of phenalenyl ligand S6 Synthesis of anionic biradicaloid K-coordinated complex.s6 NMR spectra of stoichiometric reaction..s7 NMR spectra of ligand 1 S8 NMR Spectra of heterobiarylbiaryl products.....s9-s25 S1

2 Figure S1. Perspective ORTEP view of the molecular structure of ligand 1. Thermal ellipsoids are drawn with 50% probability. Selected bond lengths (Å) and bond angels ( o ): O1-C (5); N1-C (5); N1-C (5); C1-N1-C14, 125.3(3); N1-C1-C2, 120.9(4); N1-C1-C12, 120.7(3). S2

3 Table S1. Crystal Data and Structure Refinement for Ligand 1. Identification code Ligand 1 Empirical formula C 14 H 10 NO Formula weight Temperature/K (10) Crystal system monoclinic Space group P2 1 /c a/å (6) b/å (11) c/å (4) α/ 90 β/ (3) γ/ 90 Volume/Å (6) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation Mo Kα (λ = ) 2Θ range for data collection/ 5.24 to 56.6 Index ranges -18 h 20, -4 k 5, -20 l 8 Reflections collected 3256 Independent reflections 2034 [R int = , R sigma = ] Data/restraints/parameters 2034/0/74 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = S3

4 Largest diff. peak/hole / e Å /-0.77 Table S2. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å ) for Ligand 1. U eq Is Defined as 1/3 of the Trace of the Orthogonalised U IJ Tensor. Atom x y z U(eq) O (19) 5645(8) (17) 30.9(8) N1 8961(2) 8857(8) 4049(2) 28.0(9) C1 8296(3) 7693(10) 4240(2) 26.7(5) C (3) 5616(10) 3627(2) 26.7(5) C8 6390(3) 2370(10) 3253(3) 26.7(5) C4 6830(3) 5362(10) 4639(2) 26.7(5) C9 6536(3) 1424(10) 2437(2) 26.7(5) C (3) 4658(10) 2797(2) 26.7(5) C6 5532(3) 2192(10) 4235(2) 26.7(5) C (3) 4458(10) 3842(2) 26.7(5) C (3) 10855(10) 4631(2) 30.2(10) C3 7452(3) 7390(10) 5241(2) 26.7(5) C7 5674(3) 1261(10) 3459(2) 26.7(5) C5 6109(3) 4208(10) 4817(2) 26.7(5) C (3) 2544(10) 2230(3) 26.7(5) C2 8156(3) 8472(10) 5061(2) 26.7(5) Table S3. Anisotropic Displacement Parameters (Å ) for Ligand 1. The Anisotropic Displacement Factor Exponent Takes the Form: -2π 2 [H 2 a* 2 U 11 +2hka*B*U 12 + ]. Atom U 11 U 22 U 33 U 12 U 13 U 23 O1 30.4(16) 46(2) 18.2(14) -2.2(14) 10.6(12) -4.0(12) N1 28.7(19) 35(2) 12.2(16) 1.1(17) -2.5(14) 2.1(14) C1 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C (8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) S4

5 C8 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C4 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C9 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C (8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C6 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C (8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C14 34(2) 30(2) 18(2) -3(2) -0.2(18) -3.3(17) C3 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C7 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C5 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C (8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) C2 31.6(8) 33.6(9) 10.9(7) 6.1(6) 2.5(6) 3.0(5) Table S4. Hydrogen Atom Coordinates (Å 10 4 ) and Isotropic Displacement Parameters (Å ) for Ligand 1. Atom x y z U(eq) H1 9004(2) 8380(8) 3535(2) 33.6(10) H9 6156(3) 28(10) 2050(2) 32.1(6) H6 5051(3) 1463(10) 4364(2) 32.1(6) H14a 9867(3) 12049(10) 4262(2) 36.2(12) H14b 9342(3) 12226(10) 4930(2) 36.2(12) H3 7371(3) 7990(10) 5774(2) 32.1(6) H7 5290(3) -119(10) 3069(2) 32.1(6) H5 6014(3) 4812(10) 5342(2) 32.1(6) H (3) 1908(10) 1696(3) 32.1(6) H2 8555(3) 9743(10) 5480(2) 32.1(6) S5

6 Synthesis of K-coordinated complex of phenalenyl ligand, 5: In a nitrogen filled glovebox, an oven dried 25 ml Schlenk flask was charged with ligand 1 (10 mg, mmol) and 2 equiv. of KO t Bu (5.4 mg, mmol) in benzene (2.0 ml) and the reaction mixture was stirred for 4h at room temperature under inert atmosphere. The color of the reaction mixture was changed from yellow to orange red and then the reaction mixture was dried and 1 H NMR spectroscopy of the resulting orange red solid was recorded in DMSO-d 6. 1 H NMR (DMSOd 6, 400 MHz, 298 K): δ (m,4h), 7.30 (d,2h, J = 6.8 Hz), 7.22 (d, 2H, J = 9.9 Hz), 7.04 (d, 2H, J = 9.9 Hz), 6.86 (t, 2H, J = 7.6 Hz), 6.66 (d, 2H, J = 8.4 Hz), 3.73 (s, 4H) ppm. Synthesis of anionic biradicaloid K-coordinated complex, 6: In a nitrogen filled glovebox, an oven dried 9 ml sealed tube was charged with in situ generated complex 5 (0.024 mmol) and another 2 equiv. of KO t Bu (5.4 mg, mmol) in benzene (2.0 ml) and refluxed at 130 o C for 6 hours. The color was immediately changed from orange red to dark green and the solvent was evaporated off and EPR and magnetic moment were recorded for the resulting dark green solid powder. S6

7 Figure S2. 1 H NMR spectra of stoichiometric reaction between ligand 1 and K t OBu in DMSO-d 6 : Ligand 1 + KO t Bu (1:2) Ligand 1 S7

8 Figure S3. 1 H NMR spectrum of ligand 1 in DMSO-d 6 : Figure S4. 13 C NMR Spectrum of ligand 1 in DMSO-d 6 : S8

9 NMR Spectra of Heterobiaryl Compounds: Figure S5. 1 H NMR spectrum of 4aa in CDCl 3 : Figure S6. 13 C NMR spectrum of 4aa in CDCl 3 : S9

10 Figure S7. 1 H NMR spectrum of 4ba in CDCl 3 : Figure S8. 13 C NMR spectrum of 4ba in CDCl 3 : S10

11 Figure S9. 1 H NMR spectrum of 4ca in CDCl 3 : Figure S C NMR spectrum of 4ca in CDCl 3 : S11

12 Figure S11. 1 H NMR spectrum of 4da in CDCl 3 : Figure S C NMR spectrum of 4da in CDCl 3 : S12

13 Figure S13. 1 H NMR spectrum of 4ab in CDCl 3 : Figure S C NMR spectrum of 4ab in CDCl 3 : S13

14 Figure S15. 1 H NMR spectrum of 4ea in CDCl 3 : Figure S C NMR spectrum of 4ea in CDCl 3 : S14

15 Figure S17. 1 H NMR spectrum of 4fa in CDCl 3 : Figure S C NMR spectrum of 4fa in CDCl 3 : S15

16 Figure S19. 1 H NMR spectrum of 4ga NMR in CDCl 3 : Figure S C NMR spectrum of 4ga in CDCl 3 : S16

17 Figure S21. 1 H NMR spectrum of 4ha in CDCl 3 : Figure S C NMR spectrum of 4ha in CDCl 3 : S17

18 Figure S23. 1 H NMR spectrum of 4ec in CDCl 3 : Figure S C NMR spectrum of 4ec in CDCl 3 : S18

19 Figure S25. 1 H NMR spectrum of 4ia in CDCl 3 : Figure S C NMR spectrum of 4ia in CDCl 3 : S19

20 Figure S27. 1 H NMR spectrum of 4ja in CDCl 3 : Figure S C NMR spectrum of 4ja in CDCl 3 : S20

21 Figure S29. 1 H NMR spectrum of 4ad in CDCl 3 : Figure S C NMR spectrum of 4ad in CDCl 3 : S21

22 Figure S31. 1 H NMR spectrum of 4kd in CDCl 3 : Figure S C NMR spectrum of 4kd in CDCl 3 : S22

23 Figure S33. 1 H NMR spectrum of 4ld in CDCl 3 : Figure S C NMR spectrum of 4ld in CDCl 3 : S23

24 Figure S35. 1 H NMR spectrum of 4md in CDCl 3 : Figure S C NMR spectrum of 4md in CDCl 3 : Figure S F NMR spectrum of 4md in CDCl 3 : S24

25 Figure S38. 1 H NMR spectrum of 4ed in CDCl 3 : Figure S C NMR spectrum of 4ed in CDCl 3 : Denotes solvent peaks at δ = 2.17 ppm for Acetone, δ =1.56 ppm for water, δ = 1.2 ppm and δ = ppm and for hexane impurities in 1 H NMR spectra and δ = ppm for hexane impurity in 13 C NMR spectra. S25

Sigma-spacer Regulated Thiophenyl Triazine Conjugates: Synthesis, Crystal, Zhuangli Zhu, Ersha Shao, Shan Xu, Huaming Sun, Guofang Zhang, Zunyuan

Sigma-spacer Regulated Thiophenyl Triazine Conjugates: Synthesis, Crystal, Zhuangli Zhu, Ersha Shao, Shan Xu, Huaming Sun, Guofang Zhang, Zunyuan Electronic Supplementary Supplementary Material Material (ESI) for RSC (ESI) Advances. for RSC Advances. This journal is The Royal Society of Chemistry 26 This journal is The Royal Society of Chemistry