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1 Rich coordination chemistry of π-acceptor dibenzoarsole ligands Arvind Kumar Gupta, 1 Sunisa Akkarasamiyo, 2 Andreas Orthaber*,1 1 Molecular Inorganic Chemistry, Department of Chemistry, Ångström Laboratories, Uppsala University, Box 523, Uppsala, Sweden 2 Department of Organic Chemistry, Stockholm University, Stockholm, Sweden Supporting Information S1

2 Table S1: Crystallographic data for 1, 3, 4, 5, 6, 7, 8, 9, 10 and 11 Compound Chemical formula Formula weight Temperature (K) Crystal system Space group a (Å); a ( ) b (Å); b( ) c (Å); g ( ) V (Å 3 ); Z ρ (calc.) g cm -3 μ(mo Ka) mm -1 2θmax ( ) R(int) Completeness to θ Data / param. GOF R1 [F>4σ(F)] wr2 (all data) max. peak/hole (e.å -3 ) C36H24As (2) Monoclinic P2(1)/n (11); (6);110.14(9) (12); (3); % 4452 / / C18H13As (2) Orthorhombic P2(1)2(1)2(1) 5.935(2); (3); (12); (9); % 2370 / / C36H26As (2) Monoclinic P2(1)/c (7); (3); (2) (8); (19); % 4845 / / Compound Chemical formula Formula weight Temperature (K) Crystal system Space group a (Å); a ( ) b (Å); b( ) c (Å); g ( ) V (Å 3 ); Z ρ (calc.) mg m -3 μ(mo Ka) mm -1 2θmax ( ) R(int) Completeness to θ Data / param. GOF R1 [F>4σ(F)] wr2 (all data) max. peak/hole (e.å -3 ) C32H34Cl4As2Pd (2) Trigonal R (5); (5); (16); (3); % 2476 / / C32H34Cl2As2Pd (2) Monoclinic P2(1)/n 9.643(3); (4); (10) (3); (7); % 3546 / / C36H24As2Cl2Pd (2) Monoclinic C2/c 14.26(3); (19);104.93(3) 20.49(10); (10); % 2071 / / S2

3 Compound CHCl3 Chemical formula Formula weight Temperature (K) Crystal system Space group a (Å); a ( ) b (Å); b( ) c (Å); g ( ) V (Å 3 ); Z ρ (calc.) g cm -3 μ(mo Ka) mm -1 2θmax ( ) R(int) Completeness to θ Data / param. GOF R1 [F>4σ(F)] wr2 (all data) max. peak/hole (e.å -3 ) Compound 11 Chemical formula Formula weight Temperature (K) Crystal system Space group a (Å); a ( ) b (Å); b( ) c (Å); g ( ) V (Å 3 ); Z ρ (calc.) g cm -3 μ(mo Ka) mm -1 2θmax ( ) R(int) Completeness to θ Data / param. GOF R1 [F>4σ(F)] wr2 (all data) max. peak/hole (e.å -3 ) C36H24Cl2As2Pt (2) Monoclinic C2/c (13); (10); (2) (18); (5); % 3209 / / C39H29ClAs2Pd (2) Trigonal R (4); (4); (4); (5); % 5582 / / C46H39N5Cl4As2Pd (2) Monoclinic P2/c (10); (7); (2) (12); (3); % 6843 / / C40H30Cl14As2Pd (2) Monoclinic P2(1)/c (8); (4); (3) (4); (4); % 8122 / / S3

4 Table S2: Bond lengths (Å) and angles ( ) for 1, 3, 4, 5, 6, 7, 8, 9, 10 and 11 Compound Bond lengths Bond Angles 1 As(1)-C(8); 1.915(9) As(1)-C(1); 1.937(9) As(1)-C(25); 1.955(9) As(2)-C(31); 1.936(9) C(8)-As(1)-C(1); 85.9(4) C(8)-As(1)-C(25); 100.7(4) C(1)-As(1)-C(25); 100.1(4) C(31)-As(2)-C(20); 99.9(4) As(2)-C(20); 1.937(10) C(31)-As(2)-C(13); 100.2(4) As(2)-C(13); 1.956(10) C(20)-As(2)-C(13); 85.9(4) C(2)-C(1)-C(6); 119.2(9) C(2)-C(1)-As(1); 112.1(7) C(6)-C(1)-As(1); 128.4(7) C(9)-C(8)-As(1); 128.4(8) C(7)-C(8)-As(1); 112.1(7) 3 As(1)-C(8): 1.947(3) As(1)-C(1): 1.950(3) As(1)-C(13): 1.957(3) C(8)-As(1)-C(1): 85.44(14) C(8)-As(1)-C(13): 98.92(13) C(1)-As(1)-C(13): (13) C(2)-C(1)-As(1): 126.9(3) C(6)-C(1)-As(1): 112.3(2) 4 As(1)-C(1): 1.931(6) As(1)-C(13): 1.974(5) As(2)-C(31): 1.943(5) As(2)-C(20): 1.953(5) C(14)-C(13)-As(1): 122.5(4) C(18)-C(13)-As(1): 117.7(4) C(21)-C(20)-As(2): 124.4(4) C(19)-C(20)-As(2): 116.0(3) As(2)-C(25): 1.960(5) 5 Pd(1)-Cl(2); 2.264(6) Pd(1)-Cl(1); 2.300(4) Pd(1)-As(1); 2.311(2) Pd(1)-Cl(1)#1; 2.424(4) Cl(2)-Pd(1)-Cl(1); 178.4(2) Cl(2)-Pd(1)-As(1); 83.23(16) Cl(1)-Pd(1)-As(1); 95.26(12) Cl(2)-Pd(1)-Cl(1)#1; 94.52(19) As(1)-C(1); 1.884(11) Cl(1)-Pd(1)-Cl(1)#1; 87.02(15) As(1)-C(13); 1.929(19) As(1)-Pd(1)-Cl(1)#1; (14) Cl(1)-Pd(1)#1; 2.424(4) Pd(1)-Cl(1)-Pd(1)#1; 92.97(15) 6 Pd(1)-Cl(1)#1: (4) Pd(1)-Cl(1): (4) Pd(1)-As(1): (17) Pd(1)-As(1)#1: (17) Cl(1)#1-Pd(1)-Cl(1): Cl(1)#1-Pd(1)-As(1): (11) Cl(1)-Pd(1)-As(1): (11) Cl(1)#1-Pd(1)-As(1)#1: (11) S4

5 As(1)-C(12): (16) As(1)-C(1): (15) As(1)-C(13): (16) 7 Pd(1)-Cl(1)#1: 2.358(9) Pd(1)-Cl(1): 2.358(9) Pd(1)-As(1)#1: 2.372(5) Pd(1)-As(1): 2.372(5) As(1)-C(8): 1.94(3) As(1)-C(1): 1.98(4) As(1)-C(13): 1.99(2) 8 Pt(1)-Cl(1): (10) Pt(1)-Cl(1)#1: (10) Pt(1)-As(1): (5) Pt(1)-As(1)#1: (5) As(1)-C(8): 1.922(4) As(1)-C(1): 1.927(4) As(1)-C(13): 1.964(4) Cl(1)-Pd(1)-As(1)#1: (11) As(1)-Pd(1)-As(1)#1: C(12)-As(1)-C(1): 87.98(7) C(12)-As(1)-C(13): (7) C(1)-As(1)-C(13): (7) C(12)-As(1)-Pd(1): (4) C(1)-As(1)-Pd(1): (5) C(13)-As(1)-Pd(1): (5) Cl(1)#1-Pd(1)-Cl(1): 91.8(4) Cl(1)#1-Pd(1)-As(1)#1: 175.6(2) Cl(1)-Pd(1)-As(1)#1: 88.9(3) Cl(1)#1-Pd(1)-As(1): 88.9(3) Cl(1)-Pd(1)-As(1): 175.6(2) As(1)#1-Pd(1)-As(1): 90.7(2) C(8)-As(1)-C(1): 88.0(11) C(8)-As(1)-C(13): 110.6(10) C(1)-As(1)-C(13): 103.0(10) C(8)-As(1)-Pd(1): 118.3(7) C(1)-As(1)-Pd(1): 119.1(8) C(13)-As(1)-Pd(1): 114.2(8) Cl(1)-Pt(1)-Cl(1)#1: 89.94(5) Cl(1)- Pt (1)-As(1): (3) Cl(1)#1- Pt (1)-As(1): 89.59(3) Cl(1)- Pt (1)-As(1)#1: 89.59(3) Cl(1)#1-Ir(1)-As(1)#1: (3) As(1)- Pt (1)-As(1)#1: 91.06(2) C(8)-As(1)-C(1): 88.87(18) C(8)-As(1)-C(13): (16) C(1)-As(1)-C(13): (17) C(8)-As(1)- Pt(1): (12) C(1)-As(1)- Pt(1): (11) C(13)-As(1)- Pt(1): (12) C(2)-C(1)-As(1): 129.0(3) C(6)-C(1)-As(1): 109.5(3) S5

6 9 Pd(1)-N(1): (18) Pd(1)-Cl(1): (6) Pd(1)-Cl(2): (6) Pd(1)-As(1): (3) As(1)-C(18): 1.917(2) As(1)-C(7): (19) As(1)-C(2): 1.947(2) 10 4CHCl3 Pd(1)-Cl(2): (17) Pd(1)-Cl(1): (16) Pd(1)-As(2): (8) Pd(1)-As(1): (8) As(1)-C(31): 1.919(6) As(1)-C(25): 1.934(6) As(1)-C(20): 1.947(6) As(2)-C(1): 1.925(6) As(2)-C(8): 1.931(6) As(2)-C(13): 1.952(6) N(1)-Pd(1)-Cl(1): 92.38(5) N(1)-Pd(1)-Cl(2): 90.66(5) Cl(1)-Pd(1)-Cl(2): (2) N(1)-Pd(1)-As(1): (5) Cl(1)-Pd(1)-As(1): (16) Cl(2)-Pd(1)-As(1): (16) C(18)-As(1)-C(7): 88.76(9) C(18)-As(1)-C(2): (8) C(7)-As(1)-C(2): (8) C(18)-As(1)-Pd(1): (6) C(7)-As(1)-Pd(1): (6) C(2)-As(1)-Pd(1): (6) C(3)-C(2)-As(1): (14) C(1)-C(2)-As(1): (15) C(8)-C(7)-As(1): (16) C(12)-C(7)-As(1): (14) Cl(2)-Pd(1)-Cl(1): 91.61(6) Cl(2)-Pd(1)-As(2): 89.84(5) Cl(1)-Pd(1)-As(2): (5) Cl(2)-Pd(1)-As(1): (5) Cl(1)-Pd(1)-As(1): 86.68(5) As(2)-Pd(1)-As(1): 91.75(3) C(31)-As(1)-C(25): 108.1(3) C(31)-As(1)-C(20): 105.1(3) C(25)-As(1)-C(20): 101.5(3) C(31)-As(1)-Pd(1): 110.0(2) C(25)-As(1)-Pd(1): 114.1(2) C(20)-As(1)-Pd(1): (18) C(1)-As(2)-C(8): 88.8(3) C(1)-As(2)-C(13): 110.8(3) C(8)-As(2)-C(13): 103.1(3) C(1)-As(2)-Pd(1): (19) C(8)-As(2)-Pd(1): (18) C(13)-As(2)-Pd(1): (19) S6

7 11 Pd(1)-C(35); 2.012(5) Pd(1)-As(2); (8) Pd(1)-As(1); (8) Pd(1)-Cl(1); (15) As(1)-C(8); 1.914(5) As(1)-C(1); 1.919(6) As(1)-C(13); 1.953(6) As(2)-C(16); 1.906(5) As(2)-C(23); 1.923(6) As(2)-C(28); 1.932(5) C(35)-Pd(1)-As(2); 79.43(15) C(35)-Pd(1)-As(1); 89.24(15) As(2)-Pd(1)-As(1); (3) C(35)-Pd(1)-Cl(1); (15) As(2)-Pd(1)-Cl(1); (4) As(1)-Pd(1)-Cl(1); 90.05(4) C(8)-As(1)-C(1); 88.3(2) C(8)-As(1)-C(13); 107.7(2) C(1)-As(1)-C(13); 105.2(2) C(8)-As(1)-Pd(1); (16) C(1)-As(1)-Pd(1); (16) C(13)-As(1)-Pd(1); (17) C(16)-As(2)-C(23); 88.5(3) C(16)-As(2)-C(28); 103.9(2) C(23)-As(2)-C(28); 107.2(2) C(16)-As(2)-Pd(1); (19) C(23)-As(2)-Pd(1); (18) C(28)-As(2)-Pd(1); 94.36(15) Figure S1: Single crystal X-ray structure of 7 S7

8 Figure S2: Packing diagram of 9 Figure S3: Packing diagram of 10 4CHCl3 S8

9 Figure S4: Hydrogen bonded H Cl in 10 4CHCl3 Figure S5: 1 H-NMR for 2 in CDCl3 S9

10 Figure S6: 13 C-NMR for 2 in CDCl3 Normalized Intensity Chemical Shift (ppm) Figure S7: 1 H-NMR for 4 in CDCl3 S10

11 1.0 Normalized Intensity Chemical Shift (ppm) Figure S8: 13 C-NMR for 4 in CDCl Normalized Intensity H2O DCM Chemical Shift (ppm) Figure S9: 1 H-NMR for 5 in CDCl3 S11

12 Figure S10: 13 C-NMR for 5 in CDCl3 1.0 Normalized Intensity Si- grease Chemical Shift (ppm) Figure S11: 13 C-NMR for 6 in CDCl3 S12

13 Chemical Shift (ppm) Figure S12: 13 C-NMR for 6 in CDCl3 Normalized Intensity Normalized Intensity Chemical Shift (ppm) Chemical Shift (ppm) Figure S13: Expansion of 6 Figure S14: 1 H-NMR for 7 in (CD3)2SO S13

14 Figure S15: 13 C-NMR for 7 in (CD3)2SO Figure S16: 1 H-NMR for 8 in CDCl3 S14

15 Figure S17: 13 C-NMR for 8 in CDCl3 Figure H-NMR for 10 in CDCl3 S15

16 0.050 Normalized Intensity Chemical Shift (ppm) Figure C-NMR for 11 in CDCl3. Expansion of the aromatic region. S16

17 Table S3: Nucleophilic substitution reaction with various substrates Entry Reaction Conditions comments mol% [Pd(allyl)Cl] 2 no conversion 5.5 mol% 1. toluene, rt, 1h mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 1h no conversion to the desired product. found only allyl ether 3 5 mol% [Pd(allyl)Cl] 2 11 mol% 1 toluene, rt, 2.5h 30 % conversion (crude) to: HN Ph 4 5 mol% [Pd(allyl)Cl] 2 11 mol% 1 toluene, rt, 4h 32 % conversion (crude) to: HN Ph mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 2h >99% conversion (NMR) 79% isolated yield of: mol% [Pd(allyl)Cl] 2 11 mol% 1 toluene, rt, 18h mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 4h mol% [Pd(allyl)Cl] 2 11 mol% AsPh 3 toluene, rt, 2h mol% [Pd(allyl)Cl] mol% AsPh3 toluene, rt, 2h 77% conversion (crude) of: 74% conversion (crude) of: >99% conversion of: >99% conversion (NMR) 79% isolated yield of: 10 5 mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 6h 37 % conversion (crude) to: HN Ph 11 5 mol% [Pd(allyl)Cl] 2 11 mol% AsPh 3 toluene, rt, 4h 10% conversion (crude) to: HN Ph 12 5 mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 6h no conversion S17

18 13 5 mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 6h 14 5 mol% [Pd(allyl)Cl] mol% 1 toluene, rt, 3h no conversion no conversion 1-Phenylallyl acetate [1] OAc 1-Phenylallyl acetate was synthesized according the literature report. [1] 1 H-NMR (CDCl 3, 400MHz) d (m, 5H), 6.30 (dt, J= 1.3, 5.9 Hz, 1H), 6.05 (ddd, J= 5.9, 10.4, 17.2 Hz, 1H), 5.33 (dt, J= 17.2, 1.3 Hz, 1H), 5.28 (dt, J= 10.4, 1.3 Hz, 1H), 2.14 (s, 3H); 13 C-NMR (CDCl 3, 100MHz) d 169.9, 138.9, 136.3, 128.5(2), 128.2, 127.1(2), 116.9, 76.2, 21.2 N-Cinnamylaniline [2] N H Figure S20: 1 H-NMR for 1-Phenylallyl acetate in CDCl3 S18

19 Figure S21: 13 C-NMR for 1-Phenylallyl acetate in CDCl3 Figure S22: 1 H-NMR for N-Cinnamylaniline in CDCl3 S19

20 Figure S23: 13 C-NMR for N-Cinnamylaniline in CDCl3 Figure S24: Electrochemical study of 1. Conditions WE = glassy carbon electrode, RE = Ag/AgCl, CE = Pt, DCM, TBAF 0.1 M, V = 100 mv/sec S20

21 Computational Studies : In order to assess the acceptor character of this ligand we have performed a comparative theoretical study using density functional theory (DFT) employing the M06-2X functional with a large 6-311G** basis set as implemented in the Gaussian suite of programs (G09 Rev. A.02). 3 This method is well known to perform excellently for heavier group 15 compounds. Fully optimized geometries are obtained at this level of theory and checked to be minima structures. In order to asses the acceptor character of the studied ligands we compared the energy levels of the lowest unoccupied molecular orbitals, which are a good indicator for the ease of reduction, i.e. acceptor properties. lowest unoccupied orbitals energies in ev As Figure S25 : LUMO Energies profile of triphenylphosphine, triphenylarsine, dibenzophosphole and dibenzoarsole. S21

22 Total energy : hartree Coordinates : Center Atomic Coordinates (Angstroms) Number Number X Y Z S22

23 Total energy : hartree Coordinates : Center Atomic Coordinates (Angstroms) Number Number X Y Z S23

24 Total energy : hartree Coordinates : Center Atomic Coordinates (Angstroms) Number Number X Y Z S24

25 Total energy : hartree Coordinates : Center Atomic Coordinates (Angstroms) Number Number X Y Z S25

26 References [1] Commandeur,M.; Commandeur, C.; Cossy, J. Org. Lett., 2011, 13, [2] Wang, M.; Xie, Y.; Li J.; Huang, H. Synlett 2014, 25, [3] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02, Gaussian Inc., Pittsburgh PA, S26