Functionalization of the Aryl Moiety in the Pincer Complex. (NCN)Ni III Br 2 :

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1 Electronic Supporting Information For : Functionalization of the Aryl Moiety in the Pincer Complex (NCN)Ni III Br 2 : Insights on Ni III -Promoted Carbon-Heteroatom Coupling Jean-Philippe Cloutier and Davit Zargarian* Département de chimie, Université de Montréal, Montréal (Québec), Canada H3C 3J7 zargarian.davit@umontreal.ca Table of contents : General..1 Synthesis of (NCN)Ni II Br, 1..1 Figure S1 : 1 H NMR for complex 1..2 Synthesis of (NCN)Ni III Br 2, 2 2 General protocol for functionalization of Figures S2 S11 : Mass spectra of the products of functionalization reactions Figures S12 S39 : 1 H NMR and 13 C{ 1 H} NMR spectra of organic compounds Procedure for the reaction of 2 with the radical [N(4-Br-C 6 H 4 ) 3 ][SbCl 6 ] and [NO][BF 4 ]...24 Figure S40 : Cyclovoltammetry of Figure S41: UV-vis of the reaction of 2 in MeOH..24

2 General. Unless otherwise indicated, all manipulations were carried out using standard Schlenk and glove box techniques under a dry nitrogen atmosphere using solvents dried by passage through activated aluminum oxide columns (MBraun SPS) to water contents of less than 10 ppm (determined using a Mettler-Toledo C20 coulometric Karl Fischer titrator). The reagents and substrates used in the functionalization reactions, as well as the starting materials used for the syntheses reported in this report, were purchased from Aldrich and used without further purification. 1,3-Bis(aminomethyl)benzene was used in the Eschweiler-Clarke reaction 1 to give the proligand 1,3-(Me 2 NCH 2 ) 2 C 6 H 4 (NC(H)N or a), which was then used to prepare the divalent complex {1,3-(Me 2 NCH 2 ) 2 C 6 H 3 }NiBr ((NCN)NiBr or 1). Literature procedures were used to prepare the nickel precursor NiBr 2 {NC(i-Pr)} 2 n. The NMR spectra were recorded on the following spectrometers: Bruker AV400rg ( 1 H at 400 MHz) and Bruker ARX400 ( 1 H at 400 MHz and 13 C{ 1 H} at MHz). Chemical shift values are reported in ppm ( ) and referenced internally to the residual solvent signals ( 1 H and 13 C: 7.26 and ppm for CDCl 3 ; 7.16 and ppm for C 6 D 6 ) or externally. Coupling constants are reported in Hz. The elemental analyses were performed by the Laboratoire d Analyse Élémentaire, Département de chimie, Université de Montréal. Synthesis of (NCN)Ni II Br, 1. This compound was prepared following a revised procedure reported for the synthesis of a closely related derivative (see ref. 16 in the main manuscript). An oven-dried Schlenk flask was charged with the proligand a (2.00 g, 10.4 mmol) and hexanes (15 ml). The mixture was cooled to -78 o C and n-buli (11.4 mmol, 4.6 ml) was added dropwise. The resulting red mixture was warmed to r.t. and left to stir for 2 h. Evaporation of the solvent followed by addition of THF (15 ml) gave a deep red solution, which was cannula-transferred onto a suspension of NiBr 2 {NC(i-Pr)} n (4.53 g, 12.5 mmol) THF, and stirred at r.t. for 2 h. The resulting dark brown solution was evaporated under vacuum and the product extracted with 3 x 20 ml Et 2 O. The orange solution was filtered through a pad of silica gel (5 cm) and the filtrate concentrated to ~ 5 ml to precipitate an orange solid. Addition of hexanes (60 ml) to the filtrate completed the precipitation, and filtration and washing with hexanes (3 x 10 ml) gave a bright orange powder (1.96 g, 57 %). 1 H NMR C6D6, δ 6.96 (1H, t, JHH = 7.4, H1), δ 6.39 (2H, d, JHH = 6.9, H2), δ 3.11 (4H, s, H3), δ 2.53 (12H, s, H4). Anal Calc for C 12 H 19 BrN 2 Ni (329.89): C, 43.69; N, 8.49; H, Found: C, 43.64; N, 8.39; H,

3 Figure S1. 1 H NMR (C6D6) of complex 1. δ 6.96 (1H, t, JHH = 7.4, H1), δ 6.39 (2H, d, JHH = 6.9, H2), δ 3.11 (4H, s, H3), δ 2.53 (12H, s, H4) Synthesis of (NCN)Ni III Br 2, 2. This compound was prepared using a reported procedure (see ref. 12 in the main manuscript), and has been used in the functionalization reactions. An oven-dried Schlenk flask was charged with 1 (0.500 g, 1.52 mmol) and acetone (10 ml) followed by addition of CuBr 2 (0.406 g, 1.82 mmol). The dark solution was left to stir for 15 min. The solution was then canula filtered to remove CuBr and the residue was washed with 3 x 10 ml of acetone. The combined filtrate and washings were evaporated to dryness under vacuum yielding a dark solid. This solid was extracted with 3 x 10 ml DCM and the resulting dark green extracts were evaporated to give 2 as a dark-green solid (0.549 g, 88 % yield). General procedure for the functionalization of 2. These reactions were conducted by stirring complex 2 (100 mg, mmol) in neat substrate (10 ml). The reaction mixtures were evaporated and worked up by base extraction, and the yields were determined by 1 H NMR using 1-bromo-3,5- dimethoxybenzene as standard (0.013 g, mmol). The 1 H NMR spectra used for the calibration purposes are shown on pages The results are listed in Table 1 and discussed throughout the main manuscript. 2

4 A b u n d a n c e S c a n ( m in ) : J P - N C N N I ( I I ) B R + H 2 O. D \ d a t a. m s m / z - - > Figure S2. Mass spectrum of NC(OH)N A b u n d a n c e S c a n ( m in ): C F 3 C H 2 O H y ie ld & 7 0 & 3 h & D \ d a ta.m s m / z --> Figure S3. Mass spectrum of NC(OCH2CF3)N 3

5 A b u n d a n c e S c a n ( m in ) : F A H - M E O H Y I E L D A F T E R 4 H & A C E T O N E D \ d a t a. m s m / z - - > Figure S4. Mass spectrum of NC(OMe)N A b u n d a n c e S c a n ( m i n ) : E t O H y i e l d & 7 0 & 1 h & D \ d a t a. m s m / z - - > Figure S5. Mass spectrum of NC(OEt)N 4

6 A b u n d a n c e S c a n ( m i n ) : F A H - i s o P r O H y i e l d & 7 0 & 7 h & D \ d a t a. m s m / z - - > Figure S6. Mass spectrum of NC(i-PrO)N A b u n d a n c e m / z --> S c a n ( m in ): J P -N C N N I B R 2 + N A O T B U M I N. D \ d a t a. m s Figure S7. Mass spectrum of NC(t-BuO)N 5

7 A b u n d a n c e m / z --> S c a n ( m in ): J P -N C N N I (N C C H 3 )3 + I P R N H 2. D \ d a t a. m s Figure S8. Mass spectrum of NC(i-PrNH)N A b u n d a n c e m / z --> S c a n ( m in ): J P -N C N N I(III)B R 2 + H B R.D \ d a ta.m s Figure S9. Mass spectrum of NC(Br)N 6

8 A b u n d a n c e S c a n ( m in ) : J P - N C N N I ( I I I ) B R 2 + H B R. D \ d a t a. m s m / z - - > Figure S10. Mass spectrum of NC(Cl)N A b u n d a n c e S c a n ( m in ) : J P - N C N N I ( I I I ) B R 2 + N H 4 O H. D \ d a t a. m s m / z - - > Figure S11. Mass spectrum of NC(NH2)N 7

9 Figure S12. 1 H NMR CDCl3, δ 7.01 (2H, d, JHH = 7.5, H2), δ 6.73 (1H, t, JHH = 7.5, H1), δ 3.53 (4H, s, H3), δ 2.29 (12H, s, H4), -OH proton signal was not detected. 8

10 Figure S C NMR CDCl3, δ (1C, s, C1), δ (2C, s, C3), δ (2C, s C2), δ (1C, s, C4), δ (1C, s, C7), δ (2C, s, C5) 9

11 Figure S14. 1 H NMR C6D6, δ 7.63 (2H, d, JHH = 7.5, H2), δ 7.11 (1H, t, JHH = 7.5, H1), δ 3.57 (4H, s, H3), δ 2.15 (12H, s, H4), δ 1.27 (9H, s, H5) 10

12 Figure S C NMR C6D6, δ (1C, s, C1), δ (2C, s, C3), δ (2C, s C2), δ (1C, s, C4), δ (1C, s, C7), δ (2C, s, C5), δ (4C, s, C6), δ (3C, s, C8). 11

13 Figure S16. 1 H NMR C6D6, δ 7.47 (2H, d, JHH = 7.6, H2), δ 7.05 (1H, t, JHH = 7.6, H1), δ 3.70 (3H, s, H5), δ 3.49 (4H, s, H3), δ 2.16 (12H, s, H4). Figure S C NMR C6D6, δ (1C, s, C1), δ (2C, s, C3), δ (2C, s C2), δ (1C, s, C4), δ (1C, s, C7), δ (2C, s, C5), δ (4C, s, C6) 12

14 Figure S18. 1 H NMR C6D6, δ 7.19 (2H, d, JHH = 7.5, H2), δ 6.88 (1H, t, JHH = 7.5, H1), δ 3.53 (2H, vt, JHH = 4.7, H6), δ 3.36 (2H, vt, JHH = 4.7, H5), δ 3.30 (4H, s, H3), δ 2.04 (12H, s, H4). Figure S C NMR C6D6, δ (1C, s, C1), δ (2C, s, C3), δ (2C, s C2), δ (1C, s, C4), δ (1C, s, C8), δ (2C, s, C5), δ (1C, s, C7), δ (4C, s, C6). 13

15 Figure S20. 1 H NMR spectrum of NC(H)N in CDCl3. Figure S21. 1 H NMR spectrum of NC(H)N in C6D6. 14

16 Figure S22. 1 H NMR spectrum of reaction with NH4OH 28% in C6D6. The integrated signals correspond to the NC(NH2)N product. The other products are NC(OH)N and NC(H)N. Figure S23. 1 H NMR spectrum of reaction with NH4OH 28% in CDCl3 with internal standard (integrated to 1.00). The integrated signals correspond to the NC(NH2)N (major) and NC(OH)N (minor). 15

17 Figure S24. 1 H NMR spectrum of reaction with MeNH2 33% in C6D6. The integrated signal correspond to the NC(NMeH)N product. Figure S25. 1 H NMR spectrum of reaction with MeNH2 33% with internal standard (integrated to 1.00) in C6D6. The integrated signals correspond to the NC(NMeH)N (major) and NC(OH)N (minor). 16

18 Figure S26. 1 H NMR spectrum of reaction with CF3CH2OH in C6D6. The integrated signal correspond to NC(OCH2CF3)N. The other signals correspond to NC(H)N and NC(Br)N. Figure S27. 1 H NMR spectrum of reaction with CF3CH2OH with internal standard in C6D6 (integrated to 1.00). 17

19 Figure S28. 1 H NMR spectrum of reaction with iproh in C6D6. The integrated signals correspond to NC(Oi-Pr)N. The other signals correspond to NC(H)N. Figure S29. 1 H NMR spectrum of reaction with iproh with internal standard in C6D6 (integrated to 1.00). The other signals correspond to NC(H)N. 18

20 Figure S30. 1 H NMR spectrum of reaction with HBr 48% in C6D6. The other signal correspond to NC(H)N. Figure S31. 1 H NMR spectrum of reaction with HBr 48% with internal standard in C6D6 (integrated to 1.00). The other signals correspond to NC(H)N. 19

21 Figure S32. 1 H NMR spectrum of reaction with HCl 36% in C6D6. The other signals correspond to NC(H)N. Figure S33. 1 H NMR spectrum of reaction with HCl 36% with internal standard in C6D6 (integrated to 1.00). The other signalscorrespond to NC(H)N. 20

22 Figure S34. 1 H NMR spectrum of reaction with HBF4 48% with internal standard in C6D6 (integrated to 1.00). The other signals correspond to NC(H)N. Figure S35. 1 H NMR spectrum of reaction with H2O and KBr with internal standard in CDCl3 (integrated to 1.00). The other signals correspond to NC(H)N. 21

23 Figure S36. 1 H NMR spectrum of reaction with H2O and NEt3 with internal standard in CDCl3 (integrated to 1). General procedure for the reaction of 2 with the radical [N(4-Br-C 6 H 4 ) 3 ][SbCl 6 ] and [NO][BF 4 ](Table 1). These reactions were conducted by stirring complex 2 (50 mg, mmol) in MeCN (5 ml). The reaction mixtures were evaporated and worked up by base extraction, and the yields were determined by 1 H NMR using 1-bromo-3,5-dimethoxybenzene as standard (0.013 g, mmol). 22

24 Figure S37. 1 H NMR spectrum of reaction with [N(4-Br-C 6 H 4 ) 3 ][SbCl 6 ] in C6D6. Figure S38. 1 H NMR spectrum of reaction with [N(4-Br-C 6 H 4 ) 3 ][SbCl 6 ] with internal standard in CDCl3 (integrated to 1.00). Figure S39. 1 H NMR spectrum of reaction with [NO][BF4] with internal standard in C6D6 (integrated to 1.00). 23

25 Current (ma) 2.00E E-02 Ni III /Ni IV 1.00E E E E E E (V) Figure S40. Cyclovoltammetry of 2 (1 mm) in MeCN with [NtBu4][PF6] (100 mm). Scan rate 100 mv/s. Figure S41. Time profile of the absorbance at 553 nm for the reaction of 2 (0.81 mm) in neat MeOH. The reaction was followed for 2 h. 1 Yamamoto, Y.; Chen, X.; Kojima, S.; Ohdoi, K.; Kitano, M.; Doi, Y.; Akiba, K. J. Am. Chem. Soc. 1995, 117, Vabre, B.; Spasyuk, D. M.; Zargarian, D. Organometallics 2012, 31,