Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes

Transcription

1 Supplementary Information Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes Galyna Dubinina, Hideki Furutachi, and David A. Vicic * Department of Chemistry, University of Hawaii, 2545 McCarthy Mall, Honolulu, HI and the Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University Kakuma machi, Kanazawa General Considerations. All manipulations were performed using standard Schlenk and highvacuum techniques 1 or in a nitrogen-filled dry box, unless otherwise noted. Solvents were distilled from Na/benzophenone or CaH 2. All reagents were used as received from commercial vendors unless otherwise noted. Aluminum oxide (activated, neutral, Brockmann I, ~150 mesh) and Celite were dried at 200 C under vacuum for two days prior to use. 1 H NMR spectra were recorded at ambient temperature (unless otherwise noted) on a Varian Oxford 300 MHz spectrometer and referenced to residual proton solvent peaks. 31 P spectra were recorded on the Varian Oxford spectrometer operating at 121 MHz and referenced to an 85 % phosphoric acid external standard set to 0 ppm. 19 F spectra were recorded on the Varian Oxford spectrometer operating at 282 MHz and were referenced to CFCl 3 set to zero. A Rigaku SCXMini diffractometer was used for X-ray structure determinations. Preparation of (IPr-TMS)CuCF 3 (2): To a solution of (IPr)CuOtBu (1) (0.525 g, 1.0 mmol) in THF (7 ml) was added 295 ul of CF 3 Si(CH 3 ) 3 (2.0 mmol) and the resulting reaction mixture was stirred for 24 h at ambient temperature. The mixture was evaporated under reduced pressure to give a pale pink solid. NMR yield of 2:2b was quantitative (82:18 of 2:2b). Recrystallization from toluene/pentane gave 2 as a colorless solid. 1 H NMR (CD2Cl2): δ 0.02 (s, 9H, Si(CH 3 ) 3 ), 1.23 (d, J = 6.9 Hz, 12H, CH(CH 3 ) 2 ), 1.29 (d, J = 6.9 Hz, 12H, CH(CH 3 ) 2 ), 2.47 (hept., J = 6.9 Hz, 4H, CH(CH 3 ) 2 ), 7.15 (s, 1H), 7.3 (d, J = 7.1 Hz, 4H), 7.5 (m, 2H). 19 F NMR (C 6 D 6 ): (s). Found: C 62.90%, H 7.72%, N 4.78%, Calcd for C31H44CuF3N2Si: C 62.75%, H 7.47%, N 4.72%. S1

2 ppm (f1) Figure S1: 1 H NMR spectrum of 2 in CD 2 Cl S2

3 ppm (f1) 0-50 Figure S2: 19 F NMR spectrum of 2 in CD 2 Cl (SIiPr)CuCl: A suspension of [SIiPrH][BF 4 ] 2 (1.94 g, 8 mmol), t-buok (900 mg, 8 mmol), and CuCl (900 mg, 9.1 mmol) in 30 ml THF was stirred 20 h at room temperature then filtered through a pad of Celite that was flushed two times with 7 ml of THF. The filtrate was evaporated under high vacuum, and the white residue was washed with pentane and filtered. Yield 64 %. 1 H NMR (CD 2 Cl 2 ): δ 1.23 (d, J = 6.9 Hz, 12H), 3.48 (s, 4H), 4.34 (sept., J = 6.9 Hz, 2H). [(SIiPr)CuO-t-Bu] 2 (5): A suspension of (SIiPr)CuCl (2 g, 7.9 mmol) t-buok (886.5 mg, 7.9 mmol) in 30 ml THF was stirred 2h at room temperature then filtered through a pad of Celite and washed 2 times with 7 ml of THF. The filtrate was evaporated under high vacuum. The white residue was washed with pentane and filtered. Complex 5 is thermally unstable and decomposes at room temperature in ~2 hours. Storage for days at -30 C is possible, but typically 5 was used immediately for further reactions. Yield 69 %. 1 H NMR (THF-d 8 ): δ 1.19 (s, 9H), 1.30 (s broad, 12H), 3.55 (s broad, 4H), 4.63 (s broad, 2H). S3

4 ppm (f1) Figure S3: 1 H NMR spectrum of 5 in THF-d (SIiPr)CuCF 3 (6). A solution of (SIiPr)CuOtBu (500 mg, 1.72 mmol) and CF 3 Si(CH 3 ) 3 (0.379 ml, 2.58 mmol) in 15 ml THF was stirred for 20h at room temperature. The volatiles were then evaporated on a high vacuum line. The off-white oily residue was washed two times with 5 ml of pentane. The oily product crystallized at -24 o C as a white solid over the course of 12 h. Yield 91 %. 1 H NMR (C 6 D 6 ): δ 0.91 (d, J = 6.7 Hz, 12H), 2.65 (s, 4H), 4.07 (sept, J = 6.7 Hz, 2H). 19 F NMR (C 6 D 6 ): δ (s). S4

5 CD2Cl ppm (f1) Figure S4: 1 H NMR of of (SIiPr)CuCF 3 (6) in CD 2 Cl 2. S5

6 ppm (f1) Figure S5: 19 F NMR spectrum of (SIiPr)CuCF 3 in CD 2 Cl Procedures for the trifluoromethylations: THF Method A: A resealable NMR tube was charged with complex 5 (12 mg, 0.04 mmol), internal standard (5 ul), organic halide (0.2 mmol), Me 3 Si-CF 3 (20 ul, 0.13 mmol) and 1 ml THF and kept at room temperature under nitrogen. Yields were monitored by NMR spectroscopy. THF Method B: A resealable NMR tube was charged with complex 6 (11.5 mg, 0.04 mmol), internal standard (5 ul), organic halide (0.2 mmol) and 1 ml THF and kept at room temperature under nitrogen. Yields were monitored by NMR spectroscopy. DMF Method (Table 1 in text): (SIiPr)CuOtBu (73 mg, mmol), 2 eq. of CF 3 Si(CH 3 ) 3, std. (30 μl, 0.24 mmol) were dissolved in 6 ml DMF. 1 ml aliquots (0.042 mmol of the resulting solution were taken for each reaction and 5 eq. of corresponding RHal (0.21 mmol) was added. The solutions were stirred under N 2 at room temperature. S6

7 Table S1. Trifluoromethylations mediated by 5 and 6 in THF solvent. Yields were recorded after 112 h and measured by 19 F NMR relative to 1,3-dimethyl-2-fluorobenzene as an internal standard. Yields based on copper as the limiting reagent. S7

8 X-Ray data: Figure S1: Ortep diagram of 2. Ellipsoids shown at 50 %. All hydrogens omitted for clarity. S8

9 Table S2. Crystal data and structure refinement for compound 2. Identification code compound 2 Empirical formula C31 H44 Cu F3 N2 Si Formula weight Temperature Wavelength Crystal system, space group 193(2) K A monoclinic, P21/c Unit cell dimensions a = 10.86(15) A alpha = 90 deg. b = 14.76(5) A beta = 94.8(3) deg. c = 20.36(10) A gamma = 90 deg. Volume 3252(48) A^3 Z, Calculated density 4, Mg/m^3 Absorption coefficient mm^-1 F(000) 1256 Crystal size Theta range for data collection Limiting indices 0.50 x 0.40 x 0.10 mm 1.71 to deg. -14<=h<=14, -19<=k<=19, -26<=l<=26 Reflections collected / unique / 7834 [R(int) = ] Completeness to theta = % Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 7834 / 0 / 355 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.a^-3 S9

10 Table S3. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for compound 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Cu(1) 3432(1) 8761(1) 3021(1) 39(1) Si(2) 2015(1) 11834(1) 1226(1) 40(1) F(1) 2640(2) 6984(2) 3239(1) 98(1) F(2) 4571(2) 7090(2) 3309(1) 95(1) F(3) 3582(3) 7557(2) 4088(1) 109(1) N(1) 2753(2) 10184(1) 2030(1) 30(1) N(2) 3313(2) 10739(1) 2980(1) 35(1) C(1) 3612(3) 7561(2) 3437(1) 42(1) C(2) 3192(2) 9939(2) 2654(1) 33(1) C(3) 2600(2) 11131(2) 1962(1) 33(1) C(4) 2956(2) 11454(2) 2572(1) 37(1) C(5) 2599(2) 9564(2) 1477(1) 31(1) C(6) 3654(2) 9339(2) 1152(1) 33(1) C(7) 3453(2) 8826(2) 577(1) 40(1) C(8) 2283(3) 8552(2) 342(1) 48(1) C(9) 1274(3) 8749(2) 687(1) 48(1) C(10) 1407(2) 9256(2) 1270(1) 40(1) C(11) 4952(2) 9596(2) 1419(1) 36(1) C(12) 5627(3) 8756(2) 1720(2) 50(1) C(13) 5706(2) 10034(2) 898(1) 47(1) C(14) 318(2) 9418(2) 1687(2) 54(1) C(15) 308(3) 8705(3) 2225(2) 75(1) C(16) -941(3) 9435(3) 1282(2) 80(1) C(17) 3740(3) 10848(2) 3672(1) 41(1) C(18) 4971(3) 11087(2) 3835(1) 44(1) C(19) 5329(3) 11240(2) 4504(2) 59(1) C(20) 4486(4) 11144(2) 4974(2) 71(1) C(21) 3290(4) 10897(2) 4796(1) 67(1) C(22) 2857(3) 10749(2) 4137(1) 52(1) C(23) 1531(3) 10509(3) 3956(2) 67(1) C(24) 1181(5) 9606(3) 4264(2) 97(1) C(25) 639(4) 11267(3) 4141(3) 102(2) C(26) 5907(3) 11126(2) 3313(1) 47(1) C(27) 6931(3) 11834(2) 3447(2) 64(1) C(28) 6481(3) 10195(2) 3242(2) 66(1) C(29) 301(3) 11746(3) 1069(2) 76(1) C(30) 2754(4) 11522(2) 468(1) 65(1) C(31) 2421(3) 13017(2) 1475(1) 52(1) S10

11 Table S4. Bond lengths [A] and angles [deg] for compound 2. Cu(1)-C(2) 1.902(6) Cu(1)-C(1) 1.967(6) Si(2)-C(30) 1.856(9) Si(2)-C(31) 1.862(6) Si(2)-C(29) 1.87(3) Si(2)-C(3) 1.888(7) F(1)-C(1) 1.389(11) F(2)-C(1) 1.297(12) F(3)-C(1) 1.329(7) N(1)-C(2) 1.367(7) N(1)-C(3) 1.412(5) N(1)-C(5) 1.450(5) N(2)-C(2) 1.355(5) N(2)-C(4) 1.379(5) N(2)-C(17) 1.454(7) C(3)-C(4) 1.356(7) C(4)-H(4A) C(5)-C(10) 1.403(16) C(5)-C(6) 1.411(14) C(6)-C(7) 1.396(6) C(6)-C(11) 1.516(18) C(7)-C(8) 1.380(16) C(7)-H(7A) C(8)-C(9) 1.382(13) C(8)-H(8A) C(9)-C(10) 1.400(6) C(9)-H(9A) C(10)-C(14) 1.532(14) C(11)-C(13) 1.537(9) C(11)-C(12) 1.540(7) C(11)-H(11A) C(12)-H(12A) C(12)-H(12B) C(12)-H(12C) C(13)-H(13A) C(13)-H(13B) C(13)-H(13C) C(14)-C(15) 1.519(6) C(14)-C(16) 1.536(17) C(14)-H(14A) C(15)-H(15A) C(15)-H(15B) C(15)-H(15C) C(16)-H(16A) C(16)-H(16B) C(16)-H(16C) C(17)-C(18) 1.395(18) C(17)-C(22) 1.412(11) C(18)-C(19) 1.403(7) C(18)-C(26) 1.533(12) C(19)-C(20) 1.386(11) C(19)-H(19A) C(20)-C(21) 1.368(17) S11

12 C(20)-H(20A) C(21)-C(22) 1.401(8) C(21)-H(21A) C(22)-C(23) 1.498(19) C(23)-C(24) 1.534(7) C(23)-C(25) 1.547(10) C(23)-H(23A) C(24)-H(24A) C(24)-H(24B) C(24)-H(24C) C(25)-H(25A) C(25)-H(25B) C(25)-H(25C) C(26)-C(28) 1.521(7) C(26)-C(27) 1.533(12) C(26)-H(26A) C(27)-H(27A) C(27)-H(27B) C(27)-H(27C) C(28)-H(28A) C(28)-H(28B) C(28)-H(28C) C(29)-H(29A) C(29)-H(29B) C(29)-H(29C) C(30)-H(30A) C(30)-H(30B) C(30)-H(30C) C(31)-H(31A) C(31)-H(31B) C(31)-H(31C) C(2)-Cu(1)-C(1) (11) C(30)-Si(2)-C(31) 110.5(3) C(30)-Si(2)-C(29) 109.6(5) C(31)-Si(2)-C(29) 108.8(2) C(30)-Si(2)-C(3) 112.5(4) C(31)-Si(2)-C(3) 104.1(3) C(29)-Si(2)-C(3) 111.2(3) C(2)-N(1)-C(3) 112.5(2) C(2)-N(1)-C(5) 124.2(3) C(3)-N(1)-C(5) 122.9(3) C(2)-N(2)-C(4) 111.1(3) C(2)-N(2)-C(17) 125.5(2) C(4)-N(2)-C(17) 123.3(3) F(2)-C(1)-F(3) 106.6(3) F(2)-C(1)-F(1) 102.5(8) F(3)-C(1)-F(1) 101.8(4) F(2)-C(1)-Cu(1) 116.6(3) F(3)-C(1)-Cu(1) 115.1(2) F(1)-C(1)-Cu(1) 112.5(4) N(2)-C(2)-N(1) 103.7(3) N(2)-C(2)-Cu(1) 126.8(3) N(1)-C(2)-Cu(1) (17) C(4)-C(3)-N(1) 103.7(2) C(4)-C(3)-Si(2) 125.7(3) N(1)-C(3)-Si(2) 130.6(2) S12

13 C(3)-C(4)-N(2) 109.1(3) C(3)-C(4)-H(4A) N(2)-C(4)-H(4A) C(10)-C(5)-C(6) 123.2(7) C(10)-C(5)-N(1) 118.8(3) C(6)-C(5)-N(1) 117.9(5) C(7)-C(6)-C(5) 116.5(5) C(7)-C(6)-C(11) 120.8(3) C(5)-C(6)-C(11) 122.7(7) C(8)-C(7)-C(6) 121.6(4) C(8)-C(7)-H(7A) C(6)-C(7)-H(7A) C(7)-C(8)-C(9) 120.6(7) C(7)-C(8)-H(8A) C(9)-C(8)-H(8A) C(8)-C(9)-C(10) 120.9(5) C(8)-C(9)-H(9A) C(10)-C(9)-H(9A) C(9)-C(10)-C(5) 117.1(4) C(9)-C(10)-C(14) 121.6(5) C(5)-C(10)-C(14) 121.2(7) C(6)-C(11)-C(13) 113.0(6) C(6)-C(11)-C(12) 109.7(5) C(13)-C(11)-C(12) 110.5(6) C(6)-C(11)-H(11A) C(13)-C(11)-H(11A) C(12)-C(11)-H(11A) C(11)-C(12)-H(12A) C(11)-C(12)-H(12B) H(12A)-C(12)-H(12B) C(11)-C(12)-H(12C) H(12A)-C(12)-H(12C) H(12B)-C(12)-H(12C) C(11)-C(13)-H(13A) C(11)-C(13)-H(13B) H(13A)-C(13)-H(13B) C(11)-C(13)-H(13C) H(13A)-C(13)-H(13C) H(13B)-C(13)-H(13C) C(15)-C(14)-C(10) 110.2(4) C(15)-C(14)-C(16) 109.7(4) C(10)-C(14)-C(16) 113.5(8) C(15)-C(14)-H(14A) C(10)-C(14)-H(14A) C(16)-C(14)-H(14A) C(14)-C(15)-H(15A) C(14)-C(15)-H(15B) H(15A)-C(15)-H(15B) C(14)-C(15)-H(15C) H(15A)-C(15)-H(15C) H(15B)-C(15)-H(15C) C(14)-C(16)-H(16A) C(14)-C(16)-H(16B) H(16A)-C(16)-H(16B) C(14)-C(16)-H(16C) H(16A)-C(16)-H(16C) H(16B)-C(16)-H(16C) S13

14 C(18)-C(17)-C(22) 123.9(6) C(18)-C(17)-N(2) 118.6(3) C(22)-C(17)-N(2) 117.4(7) C(17)-C(18)-C(19) 117.0(4) C(17)-C(18)-C(26) 121.5(6) C(19)-C(18)-C(26) 121.4(7) C(20)-C(19)-C(18) 120.6(7) C(20)-C(19)-H(19A) C(18)-C(19)-H(19A) C(21)-C(20)-C(19) 120.8(7) C(21)-C(20)-H(20A) C(19)-C(20)-H(20A) C(20)-C(21)-C(22) 121.9(4) C(20)-C(21)-H(21A) C(22)-C(21)-H(21A) C(21)-C(22)-C(17) 115.7(7) C(21)-C(22)-C(23) 120.8(4) C(17)-C(22)-C(23) 123.5(6) C(22)-C(23)-C(24) 111.8(4) C(22)-C(23)-C(25) 112.2(7) C(24)-C(23)-C(25) 110.3(6) C(22)-C(23)-H(23A) C(24)-C(23)-H(23A) C(25)-C(23)-H(23A) C(23)-C(24)-H(24A) C(23)-C(24)-H(24B) H(24A)-C(24)-H(24B) C(23)-C(24)-H(24C) H(24A)-C(24)-H(24C) H(24B)-C(24)-H(24C) C(23)-C(25)-H(25A) C(23)-C(25)-H(25B) H(25A)-C(25)-H(25B) C(23)-C(25)-H(25C) H(25A)-C(25)-H(25C) H(25B)-C(25)-H(25C) C(28)-C(26)-C(27) 109.6(7) C(28)-C(26)-C(18) 109.4(4) C(27)-C(26)-C(18) 114.6(6) C(28)-C(26)-H(26A) C(27)-C(26)-H(26A) C(18)-C(26)-H(26A) C(26)-C(27)-H(27A) C(26)-C(27)-H(27B) H(27A)-C(27)-H(27B) C(26)-C(27)-H(27C) H(27A)-C(27)-H(27C) H(27B)-C(27)-H(27C) C(26)-C(28)-H(28A) C(26)-C(28)-H(28B) H(28A)-C(28)-H(28B) C(26)-C(28)-H(28C) H(28A)-C(28)-H(28C) H(28B)-C(28)-H(28C) Si(2)-C(29)-H(29A) Si(2)-C(29)-H(29B) H(29A)-C(29)-H(29B) S14

15 Si(2)-C(29)-H(29C) H(29A)-C(29)-H(29C) H(29B)-C(29)-H(29C) Si(2)-C(30)-H(30A) Si(2)-C(30)-H(30B) H(30A)-C(30)-H(30B) Si(2)-C(30)-H(30C) H(30A)-C(30)-H(30C) H(30B)-C(30)-H(30C) Si(2)-C(31)-H(31A) Si(2)-C(31)-H(31B) H(31A)-C(31)-H(31B) Si(2)-C(31)-H(31C) H(31A)-C(31)-H(31C) H(31B)-C(31)-H(31C) Symmetry transformations used to generate equivalent atoms: S15

16 Table S5. Anisotropic displacement parameters (A^2 x 10^3) for compound 2. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U h k a* b* U12 ] U11 U22 U33 U23 U13 U12 Cu(1) 46(1) 36(1) 35(1) 4(1) 5(1) 0(1) Si(2) 45(1) 41(1) 34(1) 3(1) -2(1) 7(1) F(1) 91(2) 72(1) 126(2) 27(1) -17(1) -30(1) F(2) 82(2) 72(1) 132(2) 35(1) 25(1) 17(1) F(3) 202(3) 71(1) 55(1) 18(1) 16(2) -8(2) N(1) 27(1) 35(1) 29(1) -1(1) 3(1) -1(1) N(2) 41(1) 36(1) 27(1) -1(1) 3(1) 3(1) C(1) 53(2) 35(1) 40(1) 4(1) 9(1) -6(1) C(2) 32(1) 39(1) 28(1) 0(1) 5(1) -2(1) C(3) 30(1) 37(1) 33(1) -1(1) 3(1) 1(1) C(4) 43(1) 34(1) 33(1) -2(1) 1(1) 3(1) C(5) 31(1) 34(1) 29(1) -1(1) 2(1) -1(1) C(6) 34(1) 35(1) 30(1) 1(1) 4(1) -2(1) C(7) 44(1) 43(1) 34(1) -2(1) 8(1) 1(1) C(8) 55(2) 51(2) 36(1) -11(1) -3(1) -5(1) C(9) 41(1) 56(2) 46(2) -6(1) -7(1) -11(1) C(10) 32(1) 46(1) 41(1) -3(1) 0(1) -5(1) C(11) 29(1) 45(1) 35(1) -2(1) 5(1) 0(1) C(12) 37(1) 58(2) 53(2) 11(1) -1(1) 6(1) C(13) 38(1) 55(2) 48(2) 6(1) 11(1) -4(1) C(14) 26(1) 75(2) 62(2) -12(2) 6(1) -10(1) C(15) 53(2) 108(3) 67(2) 7(2) 19(2) -22(2) C(16) 29(2) 105(3) 103(3) -10(2) -2(2) -5(2) C(17) 58(2) 37(1) 27(1) -1(1) 1(1) 8(1) C(18) 56(2) 37(1) 37(1) -4(1) -7(1) 6(1) C(19) 74(2) 56(2) 44(2) -11(1) -18(2) 8(2) C(20) 108(3) 75(2) 29(2) -9(1) -7(2) 15(2) C(21) 97(3) 75(2) 32(1) -3(1) 11(2) 14(2) C(22) 70(2) 53(2) 35(1) -2(1) 9(1) 12(1) C(23) 63(2) 92(3) 47(2) 0(2) 18(2) 4(2) C(24) 101(3) 98(3) 98(3) 2(3) 36(3) -15(3) C(25) 80(3) 116(4) 112(4) 9(3) 19(3) 30(3) C(26) 43(2) 48(2) 47(2) -4(1) -7(1) 1(1) C(27) 55(2) 48(2) 87(2) -11(2) -6(2) -2(1) C(28) 61(2) 55(2) 81(2) -17(2) 7(2) 4(2) C(29) 50(2) 85(3) 88(3) 22(2) -19(2) 3(2) C(30) 103(3) 54(2) 39(2) 3(1) 9(2) 21(2) C(31) 68(2) 42(2) 46(2) 3(1) 3(1) 8(1) S16

17 Table S6. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for compound 2. x y z U(eq) H(4A) H(7A) H(8A) H(9A) H(11A) H(12A) H(12B) H(12C) H(13A) H(13B) H(13C) H(14A) H(15A) H(15B) H(15C) H(16A) H(16B) H(16C) H(19A) H(20A) H(21A) H(23A) H(24A) H(24B) H(24C) H(25A) H(25B) H(25C) H(26A) H(27A) H(27B) H(27C) H(28A) H(28B) H(28C) H(29A) H(29B) H(29C) H(30A) H(30B) H(30C) H(31A) H(31B) H(31C) S17

18 Figure S2: ORTEP diagram of 5. S18

19 Table S7. Crystal data and structure refinement for compound 5. Identification code compound 5 Empirical formula C13 H27 Cu N2 O Formula weight Temperature Wavelength 173(2) K A Crystal system, space group monoclinic, P2 1 /n Unit cell dimensions a = (4) A alpha = 90 deg. b = 8.528(3) A beta = (7) deg. c = (6) A gamma = 90 deg. Volume (9) A^3 Z, Calculated density 4, Mg/m^3 Absorption coefficient mm^-1 F(000) 624 Crystal size Theta range for data collection Limiting indices 0.37 x 0.30 x 0.15 mm 3.01 to deg. -14<=h<=14, -11<=k<=11, -21<=l<=21 Reflections collected / unique / 3565 [R(int) = ] Completeness to theta = % Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 3565 / 0 / 161 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.a^-3 S19

20 Table S8. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for compound 5. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Cu(1) 8908(1) 5795(1) 274(1) 30(1) O(1) 10576(3) 5355(4) 680(2) 36(1) N(1) 6697(3) 6209(4) 1041(2) 34(1) N(2) 7327(3) 8366(4) 521(2) 33(1) C(1) 7581(4) 6828(5) 632(2) 27(1) C(2) 5820(4) 7361(6) 1278(3) 40(1) C(3) 6154(4) 8799(5) 796(3) 41(1) C(4) 6711(4) 4601(5) 1341(3) 42(1) C(5) 6813(7) 4550(8) 2264(4) 78(2) C(6) 5645(6) 3696(7) 991(4) 63(2) C(7) 7989(4) 9391(5) 6(3) 39(1) C(8) 8446(6) 10828(7) 460(4) 69(2) C(9) 7259(6) 9782(8) -783(4) 69(2) C(10) 11083(4) 5309(6) 1484(3) 36(1) C(11) 10752(6) 3769(8) 1877(4) 65(2) C(12) 10583(5) 6682(8) 1961(3) 65(2) C(13) 12429(4) 5439(7) 1499(3) 53(1) S20

21 Table S9. Bond lengths [A] and angles [deg] for compound 5. Cu(1)-C(1) 1.858(4) Cu(1)-O(1) 1.966(3) Cu(1)-O(1)# (3) Cu(1)-Cu(1)# (12) O(1)-C(10) 1.396(5) O(1)-Cu(1)# (3) N(1)-C(1) 1.344(5) N(1)-C(4) 1.457(6) N(1)-C(2) 1.461(5) N(2)-C(1) 1.351(5) N(2)-C(7) 1.457(6) N(2)-C(3) 1.466(5) C(2)-C(3) 1.522(6) C(2)-H(1) C(2)-H(2) C(3)-H(3) C(3)-H(4) C(4)-C(6) 1.495(8) C(4)-C(5) 1.511(8) C(4)-H(5) C(5)-H(6) C(5)-H(7) C(5)-H(8) C(6)-H(9) C(6)-H(10) C(6)-H(11) C(7)-C(8) 1.503(7) C(7)-C(9) 1.514(7) C(7)-H(12) C(8)-H(22) C(8)-H(23) C(8)-H(24) C(9)-H(25) C(9)-H(26) C(9)-H(27) C(10)-C(13) 1.506(6) C(10)-C(11) 1.522(7) C(10)-C(12) 1.538(7) C(11)-H(13) C(11)-H(14) C(11)-H(15) C(12)-H(16) C(12)-H(17) C(12)-H(18) C(13)-H(19) C(13)-H(20) C(13)-H(21) C(1)-Cu(1)-O(1) (15) C(1)-Cu(1)-O(1)# (15) O(1)-Cu(1)-O(1)# (13) C(1)-Cu(1)-Cu(1)# (14) O(1)-Cu(1)-Cu(1)# (9) S21

22 O(1)#1-Cu(1)-Cu(1)# (8) C(10)-O(1)-Cu(1) 129.1(3) C(10)-O(1)-Cu(1)# (3) Cu(1)-O(1)-Cu(1)# (13) C(1)-N(1)-C(4) 123.4(4) C(1)-N(1)-C(2) 113.7(4) C(4)-N(1)-C(2) 122.2(4) C(1)-N(2)-C(7) 123.4(3) C(1)-N(2)-C(3) 112.8(4) C(7)-N(2)-C(3) 122.2(3) N(1)-C(1)-N(2) 107.1(3) N(1)-C(1)-Cu(1) 127.3(3) N(2)-C(1)-Cu(1) 125.6(3) N(1)-C(2)-C(3) 102.0(3) N(1)-C(2)-H(1) C(3)-C(2)-H(1) N(1)-C(2)-H(2) C(3)-C(2)-H(2) H(1)-C(2)-H(2) N(2)-C(3)-C(2) 102.6(3) N(2)-C(3)-H(3) C(2)-C(3)-H(3) N(2)-C(3)-H(4) C(2)-C(3)-H(4) H(3)-C(3)-H(4) N(1)-C(4)-C(6) 111.6(4) N(1)-C(4)-C(5) 111.4(5) C(6)-C(4)-C(5) 111.5(5) N(1)-C(4)-H(5) C(6)-C(4)-H(5) C(5)-C(4)-H(5) C(4)-C(5)-H(6) C(4)-C(5)-H(7) H(6)-C(5)-H(7) C(4)-C(5)-H(8) H(6)-C(5)-H(8) H(7)-C(5)-H(8) C(4)-C(6)-H(9) C(4)-C(6)-H(10) H(9)-C(6)-H(10) C(4)-C(6)-H(11) H(9)-C(6)-H(11) H(10)-C(6)-H(11) N(2)-C(7)-C(8) 111.7(4) N(2)-C(7)-C(9) 111.4(4) C(8)-C(7)-C(9) 112.7(5) N(2)-C(7)-H(12) C(8)-C(7)-H(12) C(9)-C(7)-H(12) C(7)-C(8)-H(22) C(7)-C(8)-H(23) H(22)-C(8)-H(23) C(7)-C(8)-H(24) H(22)-C(8)-H(24) H(23)-C(8)-H(24) C(7)-C(9)-H(25) C(7)-C(9)-H(26) S22

23 H(25)-C(9)-H(26) C(7)-C(9)-H(27) H(25)-C(9)-H(27) H(26)-C(9)-H(27) O(1)-C(10)-C(13) 110.2(4) O(1)-C(10)-C(11) 109.3(4) C(13)-C(10)-C(11) 109.3(5) O(1)-C(10)-C(12) 108.9(4) C(13)-C(10)-C(12) 109.7(4) C(11)-C(10)-C(12) 109.3(5) C(10)-C(11)-H(13) C(10)-C(11)-H(14) H(13)-C(11)-H(14) C(10)-C(11)-H(15) H(13)-C(11)-H(15) H(14)-C(11)-H(15) C(10)-C(12)-H(16) C(10)-C(12)-H(17) H(16)-C(12)-H(17) C(10)-C(12)-H(18) H(16)-C(12)-H(18) H(17)-C(12)-H(18) C(10)-C(13)-H(19) C(10)-C(13)-H(20) H(19)-C(13)-H(20) C(10)-C(13)-H(21) H(19)-C(13)-H(21) H(20)-C(13)-H(21) Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y+1,-z S23

24 5. Table S10. Anisotropic displacement parameters (A^2 x 10^3) for compound The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U h k a* b* U12 ] U11 U22 U33 U23 U13 U12 Cu(1) 27(1) 32(1) 35(1) 5(1) 14(1) 11(1) O(1) 25(2) 53(2) 29(2) -2(1) 3(1) 13(1) N(1) 26(2) 32(2) 46(2) 6(2) 15(2) 8(1) N(2) 27(2) 28(2) 45(2) 2(2) 13(2) 10(2) C(1) 26(2) 31(2) 24(2) 0(2) 2(2) 6(2) C(2) 30(2) 43(3) 49(3) -3(2) 17(2) 9(2) C(3) 30(2) 34(2) 62(3) 2(2) 16(2) 14(2) C(4) 36(3) 35(2) 58(3) 15(2) 13(2) 8(2) C(5) 101(6) 70(4) 63(4) 32(3) -8(4) -15(4) C(6) 61(4) 38(3) 87(5) 2(3) -3(3) 4(3) C(7) 34(3) 38(2) 45(3) 8(2) 11(2) 8(2) C(8) 74(4) 55(4) 81(5) -9(3) 31(4) -22(3) C(9) 55(4) 86(5) 65(4) 31(4) 1(3) -10(3) C(10) 29(2) 46(3) 34(2) -5(2) 8(2) 4(2) C(11) 66(4) 83(4) 47(3) 18(3) 4(3) -11(3) C(12) 58(4) 89(5) 46(3) -26(3) 2(3) 16(3) C(13) 31(3) 70(4) 56(3) -4(3) -1(2) 1(2) S24

25 Table S11. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for compound 5. x y z U(eq) H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(22) H(23) H(24) H(25) H(26) H(27) H(13) H(14) H(15) H(16) H(17) H(18) H(19) H(20) H(21) S25

26 Figure S3: ORTEP diagram of 6. Ellipsoids shown at 50 %. S26

27 Table S12. Crystal data and structure refinement for compound 6. Identification code compound 6 Empirical formula C10 H18 B Cu F3 N2 Formula weight Temperature Wavelength 173(2) K A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 8.249(3) A alpha = (7) deg. b = 9.803(3) A beta = (8) deg. c = (6) A gamma = (8) deg. Volume (8) A^3 Z, Calculated density 4, Mg/m^3 Absorption coefficient mm^-1 F(000) 612 Crystal size Theta range for data collection Limiting indices 0.45 x 0.20 x 0.20 mm 3.08 to deg. -10<=h<=10, -12<=k<=12, -21<=l<=21 Reflections collected / unique / 5932 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 5932 / 0 / 297 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.a^-3 S27

28 Table S13. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for compound 6. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Cu(1) 3532(1) 4341(1) 908(1) 36(1) Cu(2) -1751(1) 1820(1) 5029(1) 39(1) F(1) 3270(5) 2073(4) 4(2) 89(1) F(2) 1188(6) 2631(4) 764(3) 100(1) F(3) 3255(6) 1578(4) 1305(3) 98(1) F(4) -4294(5) 2909(4) 6071(2) 85(1) F(5) -3778(7) 768(5) 6273(3) 130(2) F(6) -2262(5) 2067(5) 6739(2) 100(1) N(1) 3451(4) 7275(3) 1035(2) 35(1) N(2) 5529(5) 6114(3) 1627(2) 44(1) N(3) 857(4) 2329(4) 3790(2) 38(1) N(4) -958(4) 1171(4) 3355(2) 37(1) C(1) 2669(4) 2505(3) 697(2) 15(1) C(2) 4219(5) 6017(4) 1199(3) 36(1) C(3) 5708(6) 7538(4) 1795(3) 43(1) C(4) 4251(6) 8352(4) 1370(3) 43(1) C(5) 2010(5) 7597(4) 543(3) 36(1) C(6) 672(6) 8469(5) 995(3) 50(1) C(7) 2456(6) 8306(6) -299(3) 52(1) C(8) 6703(6) 4956(4) 1900(3) 50(1) C(9) 8333(8) 5041(7) 1415(5) 90(2) C(10) 6879(9) 4867(6) 2816(4) 72(2) C(11) -3120(5) 1781(5) 6104(2) 35(1) C(12) -530(5) 1776(4) 3997(2) 33(1) C(13) 1451(6) 2145(5) 2937(3) 44(1) C(14) 280(5) 1205(5) 2660(3) 43(1) C(15) -2347(5) 345(5) 3375(3) 39(1) C(16) -1770(6) -1194(5) 3457(3) 53(1) C(17) -3349(6) 735(5) 2616(3) 51(1) C(18) 1624(6) 3204(5) 4308(3) 49(1) C(19) 3419(7) 2703(8) 4390(4) 76(2) C(20) 1328(10) 4711(6) 3983(4) 83(2) S28

29 Table S14. Bond lengths [A] and angles [deg] for compound 6. Cu(1)-C(2) 1.906(4) Cu(1)-C(1) 2.072(3) Cu(2)-C(12) 1.906(4) Cu(2)-C(11) 2.022(4) F(1)-C(1) 1.293(4) F(2)-C(1) 1.214(5) F(3)-C(1) 1.346(5) F(4)-C(11) 1.387(5) F(5)-C(11) 1.185(6) F(6)-C(11) 1.350(6) N(1)-C(2) 1.332(5) N(1)-C(5) 1.458(5) N(1)-C(4) 1.467(5) N(2)-C(2) 1.334(5) N(2)-C(8) 1.459(5) N(2)-C(3) 1.473(5) N(3)-C(12) 1.331(5) N(3)-C(13) 1.463(5) N(3)-C(18) 1.471(5) N(4)-C(12) 1.330(5) N(4)-C(15) 1.471(5) N(4)-C(14) 1.478(5) C(3)-C(4) 1.527(6) C(3)-H(1) C(3)-H(2) C(4)-H(3) C(4)-H(4) C(5)-C(7) 1.515(6) C(5)-C(6) 1.521(6) C(5)-H(5) C(6)-H(6) C(6)-H(7) C(6)-H(8) C(7)-H(9) C(7)-H(10) C(7)-H(11) C(8)-C(10) 1.495(8) C(8)-C(9) 1.524(9) C(8)-H(12) C(9)-H(13) C(9)-H(14) C(9)-H(15) C(10)-H(16) C(10)-H(17) C(10)-H(18) C(13)-C(14) 1.521(6) C(13)-H(19) C(13)-H(20) C(14)-H(21) C(14)-H(22) C(15)-C(17) 1.516(6) C(15)-C(16) 1.526(7) C(15)-H(23) S29

30 C(16)-H(24) C(16)-H(25) C(16)-H(26) C(17)-H(27) C(17)-H(28) C(17)-H(29) C(18)-C(19) 1.517(8) C(18)-C(20) 1.517(8) C(18)-H(30) C(19)-H(31) C(19)-H(32) C(19)-H(33) C(20)-H(34) C(20)-H(35) C(20)-H(36) C(2)-Cu(1)-C(1) (15) C(12)-Cu(2)-C(11) (17) C(2)-N(1)-C(5) 125.0(3) C(2)-N(1)-C(4) 113.0(3) C(5)-N(1)-C(4) 122.0(3) C(2)-N(2)-C(8) 124.9(3) C(2)-N(2)-C(3) 113.0(3) C(8)-N(2)-C(3) 122.1(3) C(12)-N(3)-C(13) 113.0(3) C(12)-N(3)-C(18) 124.6(4) C(13)-N(3)-C(18) 121.9(3) C(12)-N(4)-C(15) 124.5(3) C(12)-N(4)-C(14) 112.5(3) C(15)-N(4)-C(14) 122.2(3) F(2)-C(1)-F(1) 114.6(4) F(2)-C(1)-F(3) 109.0(4) F(1)-C(1)-F(3) 106.6(3) F(2)-C(1)-Cu(1) 109.4(3) F(1)-C(1)-Cu(1) 111.5(2) F(3)-C(1)-Cu(1) 105.2(3) N(1)-C(2)-N(2) 108.8(3) N(1)-C(2)-Cu(1) 126.0(3) N(2)-C(2)-Cu(1) 125.2(3) N(2)-C(3)-C(4) 102.3(3) N(2)-C(3)-H(1) C(4)-C(3)-H(1) N(2)-C(3)-H(2) C(4)-C(3)-H(2) H(1)-C(3)-H(2) N(1)-C(4)-C(3) 102.9(3) N(1)-C(4)-H(3) C(3)-C(4)-H(3) N(1)-C(4)-H(4) C(3)-C(4)-H(4) H(3)-C(4)-H(4) N(1)-C(5)-C(7) 110.5(3) N(1)-C(5)-C(6) 111.3(3) C(7)-C(5)-C(6) 111.1(4) N(1)-C(5)-H(5) C(7)-C(5)-H(5) C(6)-C(5)-H(5) S30

31 C(5)-C(6)-H(6) C(5)-C(6)-H(7) H(6)-C(6)-H(7) C(5)-C(6)-H(8) H(6)-C(6)-H(8) H(7)-C(6)-H(8) C(5)-C(7)-H(9) C(5)-C(7)-H(10) H(9)-C(7)-H(10) C(5)-C(7)-H(11) H(9)-C(7)-H(11) H(10)-C(7)-H(11) N(2)-C(8)-C(10) 111.1(4) N(2)-C(8)-C(9) 110.7(4) C(10)-C(8)-C(9) 112.3(5) N(2)-C(8)-H(12) C(10)-C(8)-H(12) C(9)-C(8)-H(12) C(8)-C(9)-H(13) C(8)-C(9)-H(14) H(13)-C(9)-H(14) C(8)-C(9)-H(15) H(13)-C(9)-H(15) H(14)-C(9)-H(15) C(8)-C(10)-H(16) C(8)-C(10)-H(17) H(16)-C(10)-H(17) C(8)-C(10)-H(18) H(16)-C(10)-H(18) H(17)-C(10)-H(18) F(5)-C(11)-F(6) 111.6(5) F(5)-C(11)-F(4) 108.7(4) F(6)-C(11)-F(4) 99.9(4) F(5)-C(11)-Cu(2) 114.8(3) F(6)-C(11)-Cu(2) 111.5(3) F(4)-C(11)-Cu(2) 109.2(3) N(4)-C(12)-N(3) 108.8(3) N(4)-C(12)-Cu(2) 124.2(3) N(3)-C(12)-Cu(2) 127.0(3) N(3)-C(13)-C(14) 102.6(3) N(3)-C(13)-H(19) C(14)-C(13)-H(19) N(3)-C(13)-H(20) C(14)-C(13)-H(20) H(19)-C(13)-H(20) N(4)-C(14)-C(13) 102.2(3) N(4)-C(14)-H(21) C(13)-C(14)-H(21) N(4)-C(14)-H(22) C(13)-C(14)-H(22) H(21)-C(14)-H(22) N(4)-C(15)-C(17) 111.2(3) N(4)-C(15)-C(16) 111.0(4) C(17)-C(15)-C(16) 111.0(4) N(4)-C(15)-H(23) C(17)-C(15)-H(23) C(16)-C(15)-H(23) S31

32 C(15)-C(16)-H(24) C(15)-C(16)-H(25) H(24)-C(16)-H(25) C(15)-C(16)-H(26) H(24)-C(16)-H(26) H(25)-C(16)-H(26) C(15)-C(17)-H(27) C(15)-C(17)-H(28) H(27)-C(17)-H(28) C(15)-C(17)-H(29) H(27)-C(17)-H(29) H(28)-C(17)-H(29) N(3)-C(18)-C(19) 110.4(4) N(3)-C(18)-C(20) 110.9(4) C(19)-C(18)-C(20) 113.2(5) N(3)-C(18)-H(30) C(19)-C(18)-H(30) C(20)-C(18)-H(30) C(18)-C(19)-H(31) C(18)-C(19)-H(32) H(31)-C(19)-H(32) C(18)-C(19)-H(33) H(31)-C(19)-H(33) H(32)-C(19)-H(33) C(18)-C(20)-H(34) C(18)-C(20)-H(35) H(34)-C(20)-H(35) C(18)-C(20)-H(36) H(34)-C(20)-H(36) H(35)-C(20)-H(36) Symmetry transformations used to generate equivalent atoms: S32

33 6. Table S15. Anisotropic displacement parameters (A^2 x 10^3) for compound The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U h k a* b* U12 ] U11 U22 U33 U23 U13 U12 Cu(1) 44(1) 24(1) 42(1) -6(1) -9(1) -3(1) Cu(2) 37(1) 51(1) 29(1) -9(1) 3(1) -6(1) F(1) 109(3) 91(3) 74(2) -34(2) 26(2) -37(2) F(2) 109(3) 82(3) 116(3) -36(2) 6(3) -26(2) F(3) 144(4) 57(2) 93(3) -6(2) -2(3) -14(2) F(4) 71(2) 110(3) 70(2) -18(2) 7(2) 15(2) F(5) 156(5) 98(3) 135(4) -30(3) 85(4) -38(3) F(6) 79(3) 166(4) 48(2) -8(2) 2(2) 8(3) N(1) 41(2) 24(2) 43(2) -7(1) -12(1) 0(1) N(2) 51(2) 25(2) 59(2) -8(2) -23(2) 3(1) N(3) 39(2) 46(2) 32(2) -7(1) 0(1) -13(2) N(4) 40(2) 45(2) 28(2) -8(1) 5(1) -14(2) C(1) 17(1) 13(1) 14(1) -2(1) 10(1) 2(1) C(2) 43(2) 28(2) 38(2) -5(2) -8(2) -1(2) C(3) 48(2) 29(2) 53(2) -10(2) -18(2) 1(2) C(4) 53(3) 25(2) 53(3) -9(2) -20(2) 1(2) C(5) 36(2) 32(2) 39(2) -7(2) -8(2) 3(2) C(6) 37(2) 60(3) 53(3) -17(2) -1(2) 4(2) C(7) 48(3) 67(3) 39(2) 0(2) -10(2) 1(2) C(8) 56(3) 30(2) 65(3) -5(2) -26(2) 7(2) C(9) 76(4) 75(4) 106(6) 2(4) 7(4) 36(4) C(10) 92(4) 51(3) 66(4) 9(3) -24(3) 13(3) C(11) 27(2) 49(2) 30(2) -18(2) 1(1) 5(2) C(12) 35(2) 34(2) 31(2) -2(2) -4(2) -5(2) C(13) 42(2) 57(3) 36(2) -7(2) 4(2) -16(2) C(14) 44(2) 58(3) 29(2) -9(2) 7(2) -18(2) C(15) 37(2) 48(2) 34(2) -5(2) 0(2) -15(2) C(16) 49(3) 49(3) 62(3) 12(2) -13(2) -16(2) C(17) 46(3) 47(3) 59(3) 8(2) -15(2) -12(2) C(18) 55(3) 54(3) 44(2) -13(2) -4(2) -21(2) C(19) 58(3) 107(5) 70(4) -22(4) -20(3) -22(3) C(20) 122(6) 56(3) 78(4) -13(3) -15(4) -33(4) S33

34 Table S16. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for compound 6. x y z U(eq) H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14) H(15) H(16) H(17) H(18) H(19) H(20) H(21) H(22) H(23) H(24) H(25) H(26) H(27) H(28) H(29) H(30) H(31) H(32) H(33) H(34) H(35) H(36) (1) Vicic, D. A.; Jones, G. D. In Comprehensive Organometallic Chemistry III; Crabtree, R. H., Mingos, D. M. P., Eds.; Elsevier: 2006; Vol. 1. (2) Saba, S.; Brescia, A. M.; Kaloustian, M. K. Tetrahedron Lett. 1991, 32, S34