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

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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 96822 and the Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University Kakuma machi, Kanazawa 920 1192 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 ): -33.3 (s). Found: C 62.90%, H 7.72%, N 4.78%, Calcd for C31H44CuF3N2Si: C 62.75%, H 7.47%, N 4.72%. S1

30 0.024 1.232 1.293 2.464 2.471 2.478 2.481 2.498 2.501 7.139 7.315 7.341 7.517 7.523 7.530 7.538 25 20 15 10 50 1.99 4.56 1.00 3.96 28.43 8.37 0 8.0 ppm (f1) 7.0 6.0 5.0 Figure S1: 1 H NMR spectrum of 2 in CD 2 Cl 2. 4.0 3.0 2.0 1.0 0.0 S2

-34.213 600 500 400 300 200 100 0-10 50 ppm (f1) 0-50 Figure S2: 19 F NMR spectrum of 2 in CD 2 Cl 2. -100-150 (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

4.573 3.484 1.129 1.232 40 30 20 10 2.00 4.05 12.02 8.89 0 5.0 ppm (f1) 4.0 3.0 Figure S3: 1 H NMR spectrum of 5 in THF-d 8. 2.0 1.0 (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 -33.12 (s). S4

1.241 1.264 3.482 4.331 100 500 CD2Cl2 1.73 4.00 12.13 0 ppm (f1) 5.0 4.0 3.0 2.0 1.0 Figure S4: 1 H NMR of of (SIiPr)CuCF 3 (6) in CD 2 Cl 2. S5

40-32.980 30 20 10 0 ppm (f1) 0-50 -100 Figure S5: 19 F NMR spectrum of (SIiPr)CuCF 3 in CD 2 Cl 2. -150 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, 0.251 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

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

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

Table S2. Crystal data and structure refinement for compound 2. Identification code compound 2 Empirical formula C31 H44 Cu F3 N2 Si Formula weight 593.31 Temperature Wavelength Crystal system, space group 193(2) K 0.71075 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, 1.212 Mg/m^3 Absorption coefficient 0.746 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 28.00 deg. -14<=h<=14, -19<=k<=19, -26<=l<=26 Reflections collected / unique 34736 / 7834 [R(int) = 0.0501] Completeness to theta = 28.00 99.7 % Max. and min. transmission 0.9287 and 0.7054 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 7834 / 0 / 355 Goodness-of-fit on F^2 1.060 Final R indices [I>2sigma(I)] R1 = 0.0503, wr2 = 0.1273 R indices (all data) R1 = 0.0765, wr2 = 0.1467 Largest diff. peak and hole 0.587 and -0.411 e.a^-3 S9

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

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) 0.9500 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) 0.9500 C(8)-C(9) 1.382(13) C(8)-H(8A) 0.9500 C(9)-C(10) 1.400(6) C(9)-H(9A) 0.9500 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) 1.0000 C(12)-H(12A) 0.9800 C(12)-H(12B) 0.9800 C(12)-H(12C) 0.9800 C(13)-H(13A) 0.9800 C(13)-H(13B) 0.9800 C(13)-H(13C) 0.9800 C(14)-C(15) 1.519(6) C(14)-C(16) 1.536(17) C(14)-H(14A) 1.0000 C(15)-H(15A) 0.9800 C(15)-H(15B) 0.9800 C(15)-H(15C) 0.9800 C(16)-H(16A) 0.9800 C(16)-H(16B) 0.9800 C(16)-H(16C) 0.9800 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) 0.9500 C(20)-C(21) 1.368(17) S11

C(20)-H(20A) 0.9500 C(21)-C(22) 1.401(8) C(21)-H(21A) 0.9500 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) 1.0000 C(24)-H(24A) 0.9800 C(24)-H(24B) 0.9800 C(24)-H(24C) 0.9800 C(25)-H(25A) 0.9800 C(25)-H(25B) 0.9800 C(25)-H(25C) 0.9800 C(26)-C(28) 1.521(7) C(26)-C(27) 1.533(12) C(26)-H(26A) 1.0000 C(27)-H(27A) 0.9800 C(27)-H(27B) 0.9800 C(27)-H(27C) 0.9800 C(28)-H(28A) 0.9800 C(28)-H(28B) 0.9800 C(28)-H(28C) 0.9800 C(29)-H(29A) 0.9800 C(29)-H(29B) 0.9800 C(29)-H(29C) 0.9800 C(30)-H(30A) 0.9800 C(30)-H(30B) 0.9800 C(30)-H(30C) 0.9800 C(31)-H(31A) 0.9800 C(31)-H(31B) 0.9800 C(31)-H(31C) 0.9800 C(2)-Cu(1)-C(1) 176.71(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) 129.24(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

C(3)-C(4)-N(2) 109.1(3) C(3)-C(4)-H(4A) 125.5 N(2)-C(4)-H(4A) 125.5 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) 119.2 C(6)-C(7)-H(7A) 119.2 C(7)-C(8)-C(9) 120.6(7) C(7)-C(8)-H(8A) 119.7 C(9)-C(8)-H(8A) 119.7 C(8)-C(9)-C(10) 120.9(5) C(8)-C(9)-H(9A) 119.5 C(10)-C(9)-H(9A) 119.5 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) 107.8 C(13)-C(11)-H(11A) 107.8 C(12)-C(11)-H(11A) 107.8 C(11)-C(12)-H(12A) 109.5 C(11)-C(12)-H(12B) 109.5 H(12A)-C(12)-H(12B) 109.5 C(11)-C(12)-H(12C) 109.5 H(12A)-C(12)-H(12C) 109.5 H(12B)-C(12)-H(12C) 109.5 C(11)-C(13)-H(13A) 109.5 C(11)-C(13)-H(13B) 109.5 H(13A)-C(13)-H(13B) 109.5 C(11)-C(13)-H(13C) 109.5 H(13A)-C(13)-H(13C) 109.5 H(13B)-C(13)-H(13C) 109.5 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) 107.8 C(10)-C(14)-H(14A) 107.8 C(16)-C(14)-H(14A) 107.8 C(14)-C(15)-H(15A) 109.5 C(14)-C(15)-H(15B) 109.5 H(15A)-C(15)-H(15B) 109.5 C(14)-C(15)-H(15C) 109.5 H(15A)-C(15)-H(15C) 109.5 H(15B)-C(15)-H(15C) 109.5 C(14)-C(16)-H(16A) 109.5 C(14)-C(16)-H(16B) 109.5 H(16A)-C(16)-H(16B) 109.5 C(14)-C(16)-H(16C) 109.5 H(16A)-C(16)-H(16C) 109.5 H(16B)-C(16)-H(16C) 109.5 S13

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) 119.7 C(18)-C(19)-H(19A) 119.7 C(21)-C(20)-C(19) 120.8(7) C(21)-C(20)-H(20A) 119.6 C(19)-C(20)-H(20A) 119.6 C(20)-C(21)-C(22) 121.9(4) C(20)-C(21)-H(21A) 119.0 C(22)-C(21)-H(21A) 119.0 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) 107.5 C(24)-C(23)-H(23A) 107.5 C(25)-C(23)-H(23A) 107.5 C(23)-C(24)-H(24A) 109.5 C(23)-C(24)-H(24B) 109.5 H(24A)-C(24)-H(24B) 109.5 C(23)-C(24)-H(24C) 109.5 H(24A)-C(24)-H(24C) 109.5 H(24B)-C(24)-H(24C) 109.5 C(23)-C(25)-H(25A) 109.5 C(23)-C(25)-H(25B) 109.5 H(25A)-C(25)-H(25B) 109.5 C(23)-C(25)-H(25C) 109.5 H(25A)-C(25)-H(25C) 109.5 H(25B)-C(25)-H(25C) 109.5 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) 107.7 C(27)-C(26)-H(26A) 107.7 C(18)-C(26)-H(26A) 107.7 C(26)-C(27)-H(27A) 109.5 C(26)-C(27)-H(27B) 109.5 H(27A)-C(27)-H(27B) 109.5 C(26)-C(27)-H(27C) 109.5 H(27A)-C(27)-H(27C) 109.5 H(27B)-C(27)-H(27C) 109.5 C(26)-C(28)-H(28A) 109.5 C(26)-C(28)-H(28B) 109.5 H(28A)-C(28)-H(28B) 109.5 C(26)-C(28)-H(28C) 109.5 H(28A)-C(28)-H(28C) 109.5 H(28B)-C(28)-H(28C) 109.5 Si(2)-C(29)-H(29A) 109.5 Si(2)-C(29)-H(29B) 109.5 H(29A)-C(29)-H(29B) 109.5 S14

Si(2)-C(29)-H(29C) 109.5 H(29A)-C(29)-H(29C) 109.5 H(29B)-C(29)-H(29C) 109.5 Si(2)-C(30)-H(30A) 109.5 Si(2)-C(30)-H(30B) 109.5 H(30A)-C(30)-H(30B) 109.5 Si(2)-C(30)-H(30C) 109.5 H(30A)-C(30)-H(30C) 109.5 H(30B)-C(30)-H(30C) 109.5 Si(2)-C(31)-H(31A) 109.5 Si(2)-C(31)-H(31B) 109.5 H(31A)-C(31)-H(31B) 109.5 Si(2)-C(31)-H(31C) 109.5 H(31A)-C(31)-H(31C) 109.5 H(31B)-C(31)-H(31C) 109.5 Symmetry transformations used to generate equivalent atoms: S15

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 U11 +... + 2 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

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) 2960 12074 2697 44 H(7A) 4139 8661 342 48 H(8A) 2171 8226-61 57 H(9A) 479 8536 527 58 H(11A) 4884 10048 1781 43 H(12A) 5140 8490 2055 75 H(12B) 6441 8935 1924 75 H(12C) 5729 8310 1372 75 H(13A) 5235 10536 686 70 H(13B) 5875 9581 565 70 H(13C) 6489 10262 1109 70 H(14A) 442 10021 1906 65 H(15A) 1116 8690 2478 113 H(15B) 131 8110 2024 113 H(15C) -332 8855 2519 113 H(16A) -891 9827 897 119 H(16B) -1570 9670 1555 119 H(16C) -1164 8819 1136 119 H(19A) 6157 11411 4635 71 H(20A) 4743 11251 5424 86 H(21A) 2737 10825 5130 81 H(23A) 1425 10434 3466 80 H(24A) 1720 9125 4121 146 H(24B) 319 9460 4121 146 H(24C) 1279 9656 4745 146 H(25A) 863 11837 3935 153 H(25B) 699 11340 4620 153 H(25C) -210 11103 3984 153 H(26A) 5444 11281 2882 56 H(27A) 6560 12437 3468 96 H(27B) 7485 11818 3091 96 H(27C) 7402 11698 3867 96 H(28A) 5825 9744 3155 98 H(28B) 6979 10038 3650 98 H(28C) 7009 10202 2874 98 H(29A) 11 12182 727 114 H(29B) -85 11880 1476 114 H(29C) 79 11131 922 114 H(30A) 2485 11944 113 98 H(30B) 2513 10904 337 98 H(30C) 3654 11554 555 98 H(31A) 2112 13435 1125 78 H(31B) 3321 13075 1550 78 H(31C) 2043 13165 1882 78 S17

Figure S2: ORTEP diagram of 5. S18

Table S7. Crystal data and structure refinement for compound 5. Identification code compound 5 Empirical formula C13 H27 Cu N2 O Formula weight 290.91 Temperature Wavelength 173(2) K 0.71075 A Crystal system, space group monoclinic, P2 1 /n Unit cell dimensions a = 11.170(4) A alpha = 90 deg. b = 8.528(3) A beta = 94.423(7) deg. c = 16.418(6) A gamma = 90 deg. Volume 1559.3(9) A^3 Z, Calculated density 4, 1.239 Mg/m^3 Absorption coefficient 1.390 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 27.48 deg. -14<=h<=14, -11<=k<=11, -21<=l<=21 Reflections collected / unique 15433 / 3565 [R(int) = 0.0883] Completeness to theta = 27.48 99.9 % Max. and min. transmission 0.8186 and 0.6273 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 3565 / 0 / 161 Goodness-of-fit on F^2 1.209 Final R indices [I>2sigma(I)] R1 = 0.0659, wr2 = 0.1536 R indices (all data) R1 = 0.0820, wr2 = 0.1616 Largest diff. peak and hole 1.001 and -0.478 e.a^-3 S19

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

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)#1 1.972(3) Cu(1)-Cu(1)#1 2.9906(12) O(1)-C(10) 1.396(5) O(1)-Cu(1)#1 1.972(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) 0.9900 C(2)-H(2) 0.9900 C(3)-H(3) 0.9900 C(3)-H(4) 0.9900 C(4)-C(6) 1.495(8) C(4)-C(5) 1.511(8) C(4)-H(5) 1.0000 C(5)-H(6) 0.9800 C(5)-H(7) 0.9800 C(5)-H(8) 0.9800 C(6)-H(9) 0.9800 C(6)-H(10) 0.9800 C(6)-H(11) 0.9800 C(7)-C(8) 1.503(7) C(7)-C(9) 1.514(7) C(7)-H(12) 1.0000 C(8)-H(22) 0.9800 C(8)-H(23) 0.9800 C(8)-H(24) 0.9800 C(9)-H(25) 0.9800 C(9)-H(26) 0.9800 C(9)-H(27) 0.9800 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) 0.9800 C(11)-H(14) 0.9800 C(11)-H(15) 0.9800 C(12)-H(16) 0.9800 C(12)-H(17) 0.9800 C(12)-H(18) 0.9800 C(13)-H(19) 0.9800 C(13)-H(20) 0.9800 C(13)-H(21) 0.9800 C(1)-Cu(1)-O(1) 137.85(15) C(1)-Cu(1)-O(1)#1 140.97(15) O(1)-Cu(1)-O(1)#1 81.16(13) C(1)-Cu(1)-Cu(1)#1 178.22(14) O(1)-Cu(1)-Cu(1)#1 40.65(9) S21

O(1)#1-Cu(1)-Cu(1)#1 40.51(8) C(10)-O(1)-Cu(1) 129.1(3) C(10)-O(1)-Cu(1)#1 127.9(3) Cu(1)-O(1)-Cu(1)#1 98.84(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) 111.4 C(3)-C(2)-H(1) 111.4 N(1)-C(2)-H(2) 111.4 C(3)-C(2)-H(2) 111.4 H(1)-C(2)-H(2) 109.2 N(2)-C(3)-C(2) 102.6(3) N(2)-C(3)-H(3) 111.3 C(2)-C(3)-H(3) 111.3 N(2)-C(3)-H(4) 111.3 C(2)-C(3)-H(4) 111.3 H(3)-C(3)-H(4) 109.2 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) 107.4 C(6)-C(4)-H(5) 107.4 C(5)-C(4)-H(5) 107.4 C(4)-C(5)-H(6) 109.5 C(4)-C(5)-H(7) 109.5 H(6)-C(5)-H(7) 109.5 C(4)-C(5)-H(8) 109.5 H(6)-C(5)-H(8) 109.5 H(7)-C(5)-H(8) 109.5 C(4)-C(6)-H(9) 109.5 C(4)-C(6)-H(10) 109.5 H(9)-C(6)-H(10) 109.5 C(4)-C(6)-H(11) 109.5 H(9)-C(6)-H(11) 109.5 H(10)-C(6)-H(11) 109.5 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) 106.9 C(8)-C(7)-H(12) 106.9 C(9)-C(7)-H(12) 106.9 C(7)-C(8)-H(22) 109.5 C(7)-C(8)-H(23) 109.5 H(22)-C(8)-H(23) 109.5 C(7)-C(8)-H(24) 109.5 H(22)-C(8)-H(24) 109.5 H(23)-C(8)-H(24) 109.5 C(7)-C(9)-H(25) 109.5 C(7)-C(9)-H(26) 109.5 S22

H(25)-C(9)-H(26) 109.5 C(7)-C(9)-H(27) 109.5 H(25)-C(9)-H(27) 109.5 H(26)-C(9)-H(27) 109.5 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) 109.5 C(10)-C(11)-H(14) 109.5 H(13)-C(11)-H(14) 109.5 C(10)-C(11)-H(15) 109.5 H(13)-C(11)-H(15) 109.5 H(14)-C(11)-H(15) 109.5 C(10)-C(12)-H(16) 109.5 C(10)-C(12)-H(17) 109.5 H(16)-C(12)-H(17) 109.5 C(10)-C(12)-H(18) 109.5 H(16)-C(12)-H(18) 109.5 H(17)-C(12)-H(18) 109.5 C(10)-C(13)-H(19) 109.5 C(10)-C(13)-H(20) 109.5 H(19)-C(13)-H(20) 109.5 C(10)-C(13)-H(21) 109.5 H(19)-C(13)-H(21) 109.5 H(20)-C(13)-H(21) 109.5 Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y+1,-z S23

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 U11 +... + 2 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

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) 5906 7563 1873 48 H(2) 4989 7016 1118 48 H(3) 5561 8992 326 49 H(4) 6214 9745 1146 49 H(5) 7443 4082 1152 51 H(6) 7465 5242 2475 94 H(7) 6984 3474 2447 94 H(8) 6055 4900 2468 94 H(9) 4908 4215 1135 75 H(10) 5674 2629 1214 75 H(11) 5656 3652 395 75 H(12) 8709 8792-145 47 H(22) 7767 11415 651 82 H(23) 8882 11492 96 82 H(24) 8987 10514 930 82 H(25) 6874 8827-1010 82 H(26) 7788 10216-1176 82 H(27) 6641 10555-675 82 H(13) 9876 3678 1864 78 H(14) 11094 3743 2445 78 H(15) 11074 2892 1575 78 H(16) 10761 7673 1693 77 H(17) 10958 6683 2521 77 H(18) 9712 6564 1974 77 H(19) 12744 4566 1192 63 H(20) 12775 5402 2066 63 H(21) 12644 6434 1249 63 S25

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

Table S12. Crystal data and structure refinement for compound 6. Identification code compound 6 Empirical formula C10 H18 B Cu F3 N2 Formula weight 297.61 Temperature Wavelength 173(2) K 0.71075 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 8.249(3) A alpha = 84.265(7) deg. b = 9.803(3) A beta = 86.712(8) deg. c = 16.222(6) A gamma = 83.729(8) deg. Volume 1295.9(8) A^3 Z, Calculated density 4, 1.525 Mg/m^3 Absorption coefficient 1.700 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 27.48 deg. -10<=h<=10, -12<=k<=12, -21<=l<=21 Reflections collected / unique 13604 / 5932 [R(int) = 0.0226] Completeness to theta = 27.48 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7274 and 0.5151 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 5932 / 0 / 297 Goodness-of-fit on F^2 1.076 Final R indices [I>2sigma(I)] R1 = 0.0600, wr2 = 0.1537 R indices (all data) R1 = 0.0711, wr2 = 0.1612 Largest diff. peak and hole 1.397 and -0.783 e.a^-3 S27

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

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) 0.9900 C(3)-H(2) 0.9900 C(4)-H(3) 0.9900 C(4)-H(4) 0.9900 C(5)-C(7) 1.515(6) C(5)-C(6) 1.521(6) C(5)-H(5) 1.0000 C(6)-H(6) 0.9800 C(6)-H(7) 0.9800 C(6)-H(8) 0.9800 C(7)-H(9) 0.9800 C(7)-H(10) 0.9800 C(7)-H(11) 0.9800 C(8)-C(10) 1.495(8) C(8)-C(9) 1.524(9) C(8)-H(12) 1.0000 C(9)-H(13) 0.9800 C(9)-H(14) 0.9800 C(9)-H(15) 0.9800 C(10)-H(16) 0.9800 C(10)-H(17) 0.9800 C(10)-H(18) 0.9800 C(13)-C(14) 1.521(6) C(13)-H(19) 0.9900 C(13)-H(20) 0.9900 C(14)-H(21) 0.9900 C(14)-H(22) 0.9900 C(15)-C(17) 1.516(6) C(15)-C(16) 1.526(7) C(15)-H(23) 1.0000 S29

C(16)-H(24) 0.9800 C(16)-H(25) 0.9800 C(16)-H(26) 0.9800 C(17)-H(27) 0.9800 C(17)-H(28) 0.9800 C(17)-H(29) 0.9800 C(18)-C(19) 1.517(8) C(18)-C(20) 1.517(8) C(18)-H(30) 1.0000 C(19)-H(31) 0.9800 C(19)-H(32) 0.9800 C(19)-H(33) 0.9800 C(20)-H(34) 0.9800 C(20)-H(35) 0.9800 C(20)-H(36) 0.9800 C(2)-Cu(1)-C(1) 174.71(15) C(12)-Cu(2)-C(11) 176.72(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) 111.3 C(4)-C(3)-H(1) 111.3 N(2)-C(3)-H(2) 111.3 C(4)-C(3)-H(2) 111.3 H(1)-C(3)-H(2) 109.2 N(1)-C(4)-C(3) 102.9(3) N(1)-C(4)-H(3) 111.2 C(3)-C(4)-H(3) 111.2 N(1)-C(4)-H(4) 111.2 C(3)-C(4)-H(4) 111.2 H(3)-C(4)-H(4) 109.1 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) 108.0 C(7)-C(5)-H(5) 108.0 C(6)-C(5)-H(5) 108.0 S30

C(5)-C(6)-H(6) 109.5 C(5)-C(6)-H(7) 109.5 H(6)-C(6)-H(7) 109.5 C(5)-C(6)-H(8) 109.5 H(6)-C(6)-H(8) 109.5 H(7)-C(6)-H(8) 109.5 C(5)-C(7)-H(9) 109.5 C(5)-C(7)-H(10) 109.5 H(9)-C(7)-H(10) 109.5 C(5)-C(7)-H(11) 109.5 H(9)-C(7)-H(11) 109.5 H(10)-C(7)-H(11) 109.5 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) 107.5 C(10)-C(8)-H(12) 107.5 C(9)-C(8)-H(12) 107.5 C(8)-C(9)-H(13) 109.5 C(8)-C(9)-H(14) 109.5 H(13)-C(9)-H(14) 109.5 C(8)-C(9)-H(15) 109.5 H(13)-C(9)-H(15) 109.5 H(14)-C(9)-H(15) 109.5 C(8)-C(10)-H(16) 109.5 C(8)-C(10)-H(17) 109.5 H(16)-C(10)-H(17) 109.5 C(8)-C(10)-H(18) 109.5 H(16)-C(10)-H(18) 109.5 H(17)-C(10)-H(18) 109.5 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) 111.2 C(14)-C(13)-H(19) 111.2 N(3)-C(13)-H(20) 111.2 C(14)-C(13)-H(20) 111.2 H(19)-C(13)-H(20) 109.2 N(4)-C(14)-C(13) 102.2(3) N(4)-C(14)-H(21) 111.3 C(13)-C(14)-H(21) 111.3 N(4)-C(14)-H(22) 111.3 C(13)-C(14)-H(22) 111.3 H(21)-C(14)-H(22) 109.2 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) 107.9 C(17)-C(15)-H(23) 107.9 C(16)-C(15)-H(23) 107.9 S31

C(15)-C(16)-H(24) 109.5 C(15)-C(16)-H(25) 109.5 H(24)-C(16)-H(25) 109.5 C(15)-C(16)-H(26) 109.5 H(24)-C(16)-H(26) 109.5 H(25)-C(16)-H(26) 109.5 C(15)-C(17)-H(27) 109.5 C(15)-C(17)-H(28) 109.5 H(27)-C(17)-H(28) 109.5 C(15)-C(17)-H(29) 109.5 H(27)-C(17)-H(29) 109.5 H(28)-C(17)-H(29) 109.5 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) 107.4 C(19)-C(18)-H(30) 107.4 C(20)-C(18)-H(30) 107.4 C(18)-C(19)-H(31) 109.5 C(18)-C(19)-H(32) 109.5 H(31)-C(19)-H(32) 109.5 C(18)-C(19)-H(33) 109.5 H(31)-C(19)-H(33) 109.5 H(32)-C(19)-H(33) 109.5 C(18)-C(20)-H(34) 109.5 C(18)-C(20)-H(35) 109.5 H(34)-C(20)-H(35) 109.5 C(18)-C(20)-H(36) 109.5 H(34)-C(20)-H(36) 109.5 H(35)-C(20)-H(36) 109.5 Symmetry transformations used to generate equivalent atoms: S32

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 U11 +... + 2 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

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) 6753 7838 1550 51 H(2) 5647 7634 2398 51 H(3) 3513 8842 1772 52 H(4) 4612 9029 921 52 H(5) 1582 6710 455 43 H(6) 469 8026 1555 60 H(7) -332 8557 690 60 H(8) 1015 9386 1032 60 H(9) 2803 9212-231 62 H(10) 1505 8422-644 62 H(11) 3351 7743-568 62 H(12) 6264 4093 1774 60 H(13) 8167 5052 821 108 H(14) 9091 4238 1593 108 H(15) 8789 5886 1521 108 H(16) 7322 5696 2959 86 H(17) 7623 4052 2988 86 H(18) 5808 4795 3102 86 H(19) 2590 1706 2917 53 H(20) 1390 3036 2589 53 H(21) -214 1592 2133 51 H(22) 835 273 2589 51 H(23) -3066 548 3875 47 H(24) -1132-1434 2954 64 H(25) -2719-1722 3532 64 H(26) -1090-1414 3938 64 H(27) -3690 1728 2571 61 H(28) -4318 229 2668 61 H(29) -2689 499 2119 61 H(30) 1083 3101 4876 59 H(31) 3531 1741 4628 91 H(32) 3903 3273 4753 91 H(33) 3982 2772 3841 91 H(34) 1936 4866 3451 99 H(35) 1698 5284 4383 99 H(36) 159 4958 3906 99 (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, 5031-4. S34

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