NH-Type of chiral Ni(II) complexes of glycine Schiff base: design, structural evaluation, reactivity and synthetic applications

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1 Supporting Information NH-Type of chiral Ni(II) complexes of glycine Schiff base: design, structural evaluation, reactivity and synthetic applications Mackenzie Bergagnini, a Kazunobu Fukushi, b Jianlin Han, c Norio Shibata, b Christian Roussel, d Trevor K. Ellis, a José Luis Aceña e and Vadim A. Soloshonok*,e,f a Department of Chemistry and Physics, 100 Campus Drive, Weatherford, OK , United States b Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya , Japan c School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, , China d Chirosciences, ISM2 UMR7313, Aix-Marseille University, France e Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, San Sebastián, Spain. Fax: ; Tel: ; vadym.soloshonok@ehu.es f IKERBASQUE, Basque Foundation for Science, Bilbao, Spain Table of Contents Figure 1. Thermal Ellipsoid Plot of Structure. 2 Figure 2. Packing Diagram... 3 Comments 4 Experimental... 4 Acknowledgements. 5 References... 5 Table 1. Crystal Data.. 6 Table 2. Atom Coordinates... 7 Table 3. Bond Distances and Angles.. 8 Table 4. Anisotropic Displacement Parameters.. 11 Table 5. Hydrogen Atom Parameters Table 6. Torsion Angles.. 13 NMR spectra 15

2 2

3 3

4 Comment The displacement ellipsoids were drawn at the 50% probability level. Experimental A red prism-shaped crystal of dimensions 0.47 x 0.15 x 0.13 mm was selected for structural analysis. Intensity data for this compound were collected using an instrument with a Bruker APEX ccd area detector (1) with graphite-monochromated Mo Kα radiation (λ = Å). The sample was cooled to 100(2) K. Cell parameters were determined from a non-linear least squares fit of 7600 peaks in the range 2.27 < θ < A total of 9916 data were measured in the range 1.98 < θ < using ω oscillation frames. The data were corrected for absorption by the semi-empirical method (2) giving minimum and maximum transmission factors of and The data were merged to form a set of 4890 independent data with R(int) = and a coverage of 98.7 %. The triclinic space group P 1 was determined by statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by fullmatrix least-squares methods on F 2 (3). Hydrogen atom positions were initially determined by geometry and refined by a riding model. Non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atom displacement parameters were set to 1.2 (1.5 for methyl) times the displacement parameters of the bonded atoms. A total of 331 parameters were refined against 4890 data to give wr(f 2 ) = and S = for weights of w = 1/[σ 2 (F 2 ) + ( P) P], where P = [F 2 o + 2F 2 c ] / 3. The final R(F) was for the 4458 observed, [F > 4σ(F)], data. The largest shift/s.u. was in the final refinement cycle. The final difference map had maxima and minima of and e/å 3, respectively. 4

5 Acknowledgment The authors thank the National Science Foundation (grant CHE ) and the University of Oklahoma for funds to purchase of the X-ray instrument and computers. This structure was determined by Hisanori Ueki. References (1) (a) Data Collection: SMART Software Reference Manual (1998). Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI USA. (b) Data Reduction: SAINT Software Reference Manual (1998). Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI USA. (2) G. M. Sheldrick (2002). SADABS. Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Germany. (3) (a) G. M. Sheldrick (2000). SHELXTL Version 6.10 Reference Manual. Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI USA. (b) International Tables for Crystallography, Vol C, Tables , , and , Kluwer: Boston (1995). 5

6 Table 1. Crystal data and structure refinement for Empirical formula C 28 H 28 Cl N 3 Ni O 3 Formula weight Crystal system Triclinic Space group P 1 Unit cell dimensions a = 9.263(2) Å α= (7) b = (2) Å β= (7) c = (3) Å γ= (7) Volume (5) Å 3 Z, Z' 2, 1 Density (calculated) Mg/m 3 Wavelength Å Temperature 100(2) K F(000) 572 Absorption coefficient mm -1 Absorption correction Semi-empirical from equivalents Max. and min. transmission and Theta range for data collection 1.98 to Reflections collected 9916 Independent reflections 4890 [R(int) = ] Data / restraints / parameters 4890 / 0 / 331 wr(f 2 all data) wr2 = R(F obsd data) R1 = Goodness-of-fit on F Observed data [I > 2σ(I)] 4458 Largest and mean shift / s.u and Largest diff. peak and hole and e/å wr2 = { Σ [w(f 2 o - F 2 c ) 2 ] / Σ [w(f 2 o ) 2 ] } 1/2 R1 = Σ F o - F c / Σ F o 6

7 Table 2. Atomic coordinates and equivalent isotropic displacement parameters for U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Ni(1) (3) (2) (17) (8) Cl(1) (5) (5) (4) (11) O(1) (16) (16) (12) (4) O(2) (15) (13) (10) (3) O(3) (15) (13) (11) (3) N(1) (17) (16) (12) (3) N(2) (17) (15) (12) (3) N(3) (18) (16) (12) (3) C(1) (2) (19) (15) (4) C(2) (3) (2) (17) (5) C(3) (2) (2) (16) (5) C(4) (2) (2) (16) (5) C(5) (2) (2) (15) (4) C(6) (2) (2) (15) (4) C(7) (2) (19) (14) (4) C(8) (2) (2) (15) (4) C(9) (2) (2) (15) (4) C(10) (2) (18) (14) (4) C(11) (2) (18) (14) (4) C(12) (2) (18) (14) (4) C(13) (2) (18) (14) (4) C(14) (2) (17) (14) (4) C(15) (2) (19) (15) (4) C(16) (2) (2) (15) (4) C(17) (2) (2) (16) (4) C(18) (2) (2) (16) (4) C(19) (2) (19) (15) (4) C(20) (2) (18) (14) (4) C(21) (2) (19) (15) (4) C(22) (2) (18) (15) (4) C(23) (3) (19) (16) (4) C(24) (3) (2) (18) (5) C(25) (3) (2) (18) (5) C(26) (2) (2) (17) (5) C(27) (2) (19) (15) (4) C(28) (2) (18) (15) (4) 7

8 Table 3. Bond lengths [Å] and angles [ ] for Ni(1)-N(1) (16) Ni(1)-N(2) (16) Ni(1)-O(2) (13) Ni(1)-N(3) (17) Cl(1)-C(10) 1.745(2) O(1)-C(6) 1.224(2) O(2)-C(28) 1.287(2) O(3)-C(28) 1.230(2) N(1)-C(6) 1.370(2) N(1)-C(7) 1.393(3) N(2)-C(13) 1.293(3) N(2)-C(20) 1.474(2) N(3)-C(5) 1.484(2) N(3)-C(1) 1.519(2) N(3)-H(3N) 0.80(2) C(1)-C(4) 1.521(3) C(1)-C(2) 1.527(3) C(1)-C(3) 1.535(3) C(2)-H(2A) C(2)-H(2B) C(2)-H(2C) C(3)-H(3A) C(3)-H(3B) C(3)-H(3C) C(4)-H(4A) C(4)-H(4B) C(4)-H(4C) C(5)-C(6) 1.519(3) C(5)-H(5A) C(5)-H(5B) C(7)-C(8) 1.410(3) C(7)-C(12) 1.421(3) C(8)-C(9) 1.377(3) C(8)-H(8) C(9)-C(10) 1.388(3) N(1)-Ni(1)-N(2) 93.68(7) N(1)-Ni(1)-O(2) (7) N(2)-Ni(1)-O(2) 86.35(6) N(1)-Ni(1)-N(3) 86.36(7) N(2)-Ni(1)-N(3) (7) O(2)-Ni(1)-N(3) 93.59(7) C(28)-O(2)-Ni(1) (12) C(6)-N(1)-C(7) (16) C(6)-N(1)-Ni(1) (13) 8 C(9)-H(9) C(10)-C(11) 1.373(3) C(11)-C(12) 1.410(3) C(11)-H(11) C(12)-C(13) 1.465(3) C(13)-C(14) 1.498(2) C(14)-C(15) 1.392(3) C(14)-C(19) 1.394(3) C(15)-C(16) 1.390(3) C(15)-H(15) C(16)-C(17) 1.381(3) C(16)-H(16) C(17)-C(18) 1.385(3) C(17)-H(17) C(18)-C(19) 1.385(3) C(18)-H(18) C(19)-H(19) C(20)-C(28) 1.528(3) C(20)-C(21) 1.553(3) C(20)-H(20) C(21)-C(22) 1.517(3) C(21)-H(21A) C(21)-H(21B) C(22)-C(23) 1.392(3) C(22)-C(27) 1.394(3) C(23)-C(24) 1.389(3) C(23)-H(23) C(24)-C(25) 1.387(3) C(24)-H(24) C(25)-C(26) 1.381(3) C(25)-H(25) C(26)-C(27) 1.392(3) C(26)-H(26) C(27)-H(27) C(7)-N(1)-Ni(1) (13) C(13)-N(2)-C(20) (16) C(13)-N(2)-Ni(1) (13) C(20)-N(2)-Ni(1) (12) C(5)-N(3)-C(1) (15) C(5)-N(3)-Ni(1) (12) C(1)-N(3)-Ni(1) (12) C(5)-N(3)-H(3N) 110.4(17) C(1)-N(3)-H(3N) 105.6(17)

9 Ni(1)-N(3)-H(3N) 103.9(17) N(3)-C(1)-C(4) (16) N(3)-C(1)-C(2) (16) C(4)-C(1)-C(2) (18) N(3)-C(1)-C(3) (16) C(4)-C(1)-C(3) (17) C(2)-C(1)-C(3) (17) C(1)-C(2)-H(2A) C(1)-C(2)-H(2B) H(2A)-C(2)-H(2B) C(1)-C(2)-H(2C) H(2A)-C(2)-H(2C) H(2B)-C(2)-H(2C) C(1)-C(3)-H(3A) C(1)-C(3)-H(3B) H(3A)-C(3)-H(3B) C(1)-C(3)-H(3C) H(3A)-C(3)-H(3C) H(3B)-C(3)-H(3C) C(1)-C(4)-H(4A) C(1)-C(4)-H(4B) H(4A)-C(4)-H(4B) C(1)-C(4)-H(4C) H(4A)-C(4)-H(4C) H(4B)-C(4)-H(4C) N(3)-C(5)-C(6) (16) N(3)-C(5)-H(5A) C(6)-C(5)-H(5A) N(3)-C(5)-H(5B) C(6)-C(5)-H(5B) H(5A)-C(5)-H(5B) O(1)-C(6)-N(1) (19) O(1)-C(6)-C(5) (18) N(1)-C(6)-C(5) (16) N(1)-C(7)-C(8) (17) N(1)-C(7)-C(12) (17) C(8)-C(7)-C(12) (18) C(9)-C(8)-C(7) (19) C(9)-C(8)-H(8) C(7)-C(8)-H(8) C(8)-C(9)-C(10) (18) C(8)-C(9)-H(9) C(10)-C(9)-H(9) C(11)-C(10)-C(9) (18) C(11)-C(10)-Cl(1) (15) C(9)-C(10)-Cl(1) (15) C(10)-C(11)-C(12) (18) C(10)-C(11)-H(11) C(12)-C(11)-H(11) C(11)-C(12)-C(7) (17) C(11)-C(12)-C(13) (17) C(7)-C(12)-C(13) (17) N(2)-C(13)-C(12) (17) N(2)-C(13)-C(14) (16) C(12)-C(13)-C(14) (16) C(15)-C(14)-C(19) (18) C(15)-C(14)-C(13) (17) C(19)-C(14)-C(13) (17) C(16)-C(15)-C(14) (18) C(16)-C(15)-H(15) C(14)-C(15)-H(15) C(17)-C(16)-C(15) (18) C(17)-C(16)-H(16) C(15)-C(16)-H(16) C(16)-C(17)-C(18) (19) C(16)-C(17)-H(17) C(18)-C(17)-H(17) C(19)-C(18)-C(17) (19) C(19)-C(18)-H(18) C(17)-C(18)-H(18) C(18)-C(19)-C(14) (18) C(18)-C(19)-H(19) C(14)-C(19)-H(19) N(2)-C(20)-C(28) (15) N(2)-C(20)-C(21) (15) C(28)-C(20)-C(21) (16) N(2)-C(20)-H(20) C(28)-C(20)-H(20) C(21)-C(20)-H(20) C(22)-C(21)-C(20) (16) C(22)-C(21)-H(21A) C(20)-C(21)-H(21A) C(22)-C(21)-H(21B) C(20)-C(21)-H(21B) H(21A)-C(21)-H(21B) C(23)-C(22)-C(27) 118.4(2) C(23)-C(22)-C(21) (19) C(27)-C(22)-C(21) (18) C(24)-C(23)-C(22) 121.2(2) C(24)-C(23)-H(23) C(22)-C(23)-H(23) C(25)-C(24)-C(23) 119.9(2) C(25)-C(24)-H(24) C(23)-C(24)-H(24) C(26)-C(25)-C(24) 119.5(2) C(26)-C(25)-H(25) 120.2

10 C(24)-C(25)-H(25) C(25)-C(26)-C(27) 120.6(2) C(25)-C(26)-H(26) C(27)-C(26)-H(26) C(26)-C(27)-C(22) 120.3(2) C(26)-C(27)-H(27) C(22)-C(27)-H(27) O(3)-C(28)-O(2) (18) O(3)-C(28)-C(20) (17) O(2)-C(28)-C(20) (16) 10

11 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for The anisotropic displacement factor exponent takes the form: -2 π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Ni(1) 11(1) 16(1) 11(1) -1(1) -1(1) -3(1) Cl(1) 18(1) 19(1) 21(1) -6(1) -4(1) -1(1) O(1) 15(1) 43(1) 27(1) -9(1) -6(1) -4(1) O(2) 15(1) 21(1) 15(1) -2(1) -2(1) -3(1) O(3) 15(1) 21(1) 23(1) -7(1) -4(1) -4(1) N(1) 13(1) 20(1) 14(1) -1(1) -2(1) -3(1) N(2) 13(1) 16(1) 14(1) 0(1) -5(1) -2(1) N(3) 15(1) 15(1) 15(1) -2(1) -2(1) -2(1) C(1) 23(1) 18(1) 14(1) 0(1) 1(1) -1(1) C(2) 39(1) 16(1) 21(1) -1(1) 2(1) -1(1) C(3) 25(1) 25(1) 18(1) -1(1) 4(1) -4(1) C(4) 25(1) 30(1) 21(1) 5(1) -4(1) 3(1) C(5) 11(1) 24(1) 20(1) -2(1) -2(1) -2(1) C(6) 14(1) 23(1) 20(1) 1(1) -3(1) -3(1) C(7) 17(1) 19(1) 13(1) 1(1) -5(1) -3(1) C(8) 15(1) 28(1) 18(1) -2(1) -1(1) -7(1) C(9) 21(1) 22(1) 18(1) -1(1) -6(1) -8(1) C(10) 18(1) 17(1) 13(1) -3(1) -4(1) 0(1) C(11) 14(1) 19(1) 12(1) 1(1) -4(1) -1(1) C(12) 14(1) 17(1) 12(1) 3(1) -5(1) -3(1) C(13) 13(1) 17(1) 12(1) 2(1) -3(1) 1(1) C(14) 15(1) 13(1) 14(1) -3(1) -2(1) -3(1) C(15) 14(1) 25(1) 17(1) -1(1) -5(1) 1(1) C(16) 20(1) 34(1) 13(1) 2(1) -2(1) 0(1) C(17) 14(1) 34(1) 19(1) -1(1) 2(1) 1(1) C(18) 15(1) 29(1) 22(1) 0(1) -5(1) 2(1) C(19) 18(1) 22(1) 15(1) 1(1) -4(1) -2(1) C(20) 14(1) 17(1) 18(1) -2(1) -2(1) -4(1) C(21) 25(1) 18(1) 15(1) 0(1) -2(1) -5(1) C(22) 26(1) 13(1) 19(1) 3(1) -6(1) -2(1) C(23) 32(1) 18(1) 20(1) -1(1) -9(1) 1(1) C(24) 35(1) 24(1) 34(1) 1(1) -21(1) -1(1) C(25) 22(1) 24(1) 38(1) 5(1) -12(1) 2(1) C(26) 27(1) 21(1) 26(1) 2(1) -4(1) 4(1) C(27) 25(1) 20(1) 18(1) 0(1) -6(1) -1(1) C(28) 15(1) 17(1) 18(1) -4(1) -3(1) 2(1) 11

12 Table 5. Hydrogen coordinates and isotropic displacement parameters for x y z U(eq) H(3N) 0.730(3) 0.175(2) (18) H(2A) H(2B) H(2C) H(3A) H(3B) H(3C) H(4A) H(4B) H(4C) H(5A) H(5B) H(8) H(9) H(11) H(15) H(16) H(17) H(18) H(19) H(20) H(21A) H(21B) H(23) H(24) H(25) H(26) H(27)

13 Table 6. Torsion angles [ ] for N(1)-Ni(1)-O(2)-C(28) 80(13) N(2)-Ni(1)-O(2)-C(28) (13) N(3)-Ni(1)-O(2)-C(28) (13) N(2)-Ni(1)-N(1)-C(6) (14) O(2)-Ni(1)-N(1)-C(6) 56(13) N(3)-Ni(1)-N(1)-C(6) (14) N(2)-Ni(1)-N(1)-C(7) (15) O(2)-Ni(1)-N(1)-C(7) -126(13) N(3)-Ni(1)-N(1)-C(7) (15) N(1)-Ni(1)-N(2)-C(13) 21.38(17) O(2)-Ni(1)-N(2)-C(13) (17) N(3)-Ni(1)-N(2)-C(13) 111.9(11) N(1)-Ni(1)-N(2)-C(20) (12) O(2)-Ni(1)-N(2)-C(20) 24.44(12) N(3)-Ni(1)-N(2)-C(20) -64.8(11) N(1)-Ni(1)-N(3)-C(5) 32.10(12) N(2)-Ni(1)-N(3)-C(5) -58.6(11) O(2)-Ni(1)-N(3)-C(5) (12) N(1)-Ni(1)-N(3)-C(1) (14) N(2)-Ni(1)-N(3)-C(1) 173.5(10) O(2)-Ni(1)-N(3)-C(1) 84.56(14) C(5)-N(3)-C(1)-C(4) (16) Ni(1)-N(3)-C(1)-C(4) (19) C(5)-N(3)-C(1)-C(2) -57.3(2) Ni(1)-N(3)-C(1)-C(2) 65.85(19) C(5)-N(3)-C(1)-C(3) 64.7(2) Ni(1)-N(3)-C(1)-C(3) (13) C(1)-N(3)-C(5)-C(6) 96.75(19) Ni(1)-N(3)-C(5)-C(6) (17) C(7)-N(1)-C(6)-O(1) 12.8(3) Ni(1)-N(1)-C(6)-O(1) (18) C(7)-N(1)-C(6)-C(5) (16) Ni(1)-N(1)-C(6)-C(5) 9.9(2) N(3)-C(5)-C(6)-O(1) (18) N(3)-C(5)-C(6)-N(1) 17.1(2) C(6)-N(1)-C(7)-C(8) 26.0(3) Ni(1)-N(1)-C(7)-C(8) (15) C(6)-N(1)-C(7)-C(12) (18) Ni(1)-N(1)-C(7)-C(12) 23.4(2) N(1)-C(7)-C(8)-C(9) (18) C(12)-C(7)-C(8)-C(9) -0.2(3) C(7)-C(8)-C(9)-C(10) 2.4(3) C(8)-C(9)-C(10)-C(11) -2.3(3) C(8)-C(9)-C(10)-Cl(1) (15) C(9)-C(10)-C(11)-C(12) 0.0(3) 13 Cl(1)-C(10)-C(11)-C(12) (14) C(10)-C(11)-C(12)-C(7) 2.3(3) C(10)-C(11)-C(12)-C(13) (17) N(1)-C(7)-C(12)-C(11) (16) C(8)-C(7)-C(12)-C(11) -2.2(3) N(1)-C(7)-C(12)-C(13) 2.1(3) C(8)-C(7)-C(12)-C(13) (17) C(20)-N(2)-C(13)-C(12) (16) Ni(1)-N(2)-C(13)-C(12) -4.3(3) C(20)-N(2)-C(13)-C(14) -11.6(3) Ni(1)-N(2)-C(13)-C(14) (13) C(11)-C(12)-C(13)-N(2) (17) C(7)-C(12)-C(13)-N(2) -12.2(3) C(11)-C(12)-C(13)-C(14) -8.6(2) C(7)-C(12)-C(13)-C(14) (16) N(2)-C(13)-C(14)-C(15) 106.8(2) C(12)-C(13)-C(14)-C(15) -76.6(2) N(2)-C(13)-C(14)-C(19) -75.1(2) C(12)-C(13)-C(14)-C(19) 101.5(2) C(19)-C(14)-C(15)-C(16) -1.0(3) C(13)-C(14)-C(15)-C(16) (18) C(14)-C(15)-C(16)-C(17) -0.2(3) C(15)-C(16)-C(17)-C(18) 1.2(3) C(16)-C(17)-C(18)-C(19) -0.9(3) C(17)-C(18)-C(19)-C(14) -0.3(3) C(15)-C(14)-C(19)-C(18) 1.3(3) C(13)-C(14)-C(19)-C(18) (18) C(13)-N(2)-C(20)-C(28) (17) Ni(1)-N(2)-C(20)-C(28) (17) C(13)-N(2)-C(20)-C(21) -83.5(2) Ni(1)-N(2)-C(20)-C(21) 93.44(15) N(2)-C(20)-C(21)-C(22) -43.1(2) C(28)-C(20)-C(21)-C(22) 75.5(2) C(20)-C(21)-C(22)-C(23) 105.0(2) C(20)-C(21)-C(22)-C(27) -73.1(2) C(27)-C(22)-C(23)-C(24) 0.8(3) C(21)-C(22)-C(23)-C(24) (18) C(22)-C(23)-C(24)-C(25) -1.1(3) C(23)-C(24)-C(25)-C(26) 0.2(3) C(24)-C(25)-C(26)-C(27) 1.0(3) C(25)-C(26)-C(27)-C(22) -1.3(3) C(23)-C(22)-C(27)-C(26) 0.3(3) C(21)-C(22)-C(27)-C(26) (18) Ni(1)-O(2)-C(28)-O(3) (16) Ni(1)-O(2)-C(28)-C(20) 2.6(2)

14 N(2)-C(20)-C(28)-O(3) (17) C(21)-C(20)-C(28)-O(3) 74.8(2) N(2)-C(20)-C(28)-O(2) 16.3(2) C(21)-C(20)-C(28)-O(2) (19) 14

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43 NHtbutylMichaelwithipropyl 10 1 "C:\Users\Ellis\My NMR Files\ICON-NMR Data" PROTON [rel] [ppm]

44 NHtbutylmichaelwithalphanaphthyl 10 1 "C:\Users\Ellis\My NMR Files\ICON-NMR Data" PROTON [rel] [ppm]

45 NHtButlymichaelwith4CF3Ph 10 1 "C:\Users\Hubin\My NMR Files\ICON-NMR Data" PROTON [rel] [ppm]

46 NHtbutylMichaelwith4OMePH 10 1 "C:\Users\Ellis\My NMR Files\ICON-NMR Data" PROTON [rel] [ppm]

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49 f1 (ppm)