# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'D. W. Stephan' _publ_contact_author_address ; Department of Chemistry University of Toronto 80 St George St. Toronto Ontario M5S 3H6 CANADA ; _publ_contact_author_email DSTEPHAN@CHEM.UTORONTO.CA _publ_section_title ; Lewis acid catalyzed hydrogenation: B(C6F5)3 mediated reduction of imines and nitriles with H2 ; loop_ _publ_author_name 'D. W. Stephan' 'Preston A. Chase' 'Titel Jurca' data_[tBuNH2(CH2Ph)][B(C6F5)3H] _database_code_depnum_ccdc_archive 'CCDC 669400' _audit_creation_method SHELXL-97 _chemical_formula_sum 'C29 H19 B F15 N' _chemical_formula_weight 677.26 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monomclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 10.2932(10) _cell_length_b 13.9127(14) _cell_length_c 20.747(2) _cell_angle_alpha 90.00 _cell_angle_beta 104.0340(10) _cell_angle_gamma 90.00 _cell_volume 2882.4(5) _cell_formula_units_Z 4 _cell_measurement_temperature 273(2) _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 25.0 _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.21 _exptl_crystal_density_diffrn 1.561 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1360 _exptl_absorpt_coefficient_mu 0.159 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.858567 _exptl_absorpt_correction_T_max 1.00000 _diffrn_ambient_temperature 273(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_reflns_number 27210 _diffrn_reflns_av_R_equivalents 0.0440 _diffrn_reflns_av_sigmaI/netI 0.0336 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5088 _reflns_number_gt 3004 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0594P)^2^+0.3134P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_number_reflns 5088 _refine_ls_number_parameters 427 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0869 _refine_ls_R_factor_gt 0.0442 _refine_ls_wR_factor_ref 0.1228 _refine_ls_wR_factor_gt 0.1006 _refine_ls_goodness_of_fit_ref 0.998 _refine_ls_restrained_S_all 0.998 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group B1 B 0.4788(3) 0.2275(2) 0.13550(13) 0.0523(6) Uani 1 1 d . . . H1 H 0.5344(18) 0.2007(13) 0.1881(9) 0.047(5) Uiso 1 1 d . . . F1 F 0.75007(14) 0.14498(12) 0.16698(8) 0.0864(5) Uani 1 1 d . . . F2 F 0.94368(15) 0.18083(14) 0.10637(9) 0.1107(6) Uani 1 1 d . . . F3 F 0.90033(18) 0.30239(15) 0.00044(10) 0.1206(7) Uani 1 1 d . . . F4 F 0.6590(2) 0.38830(15) -0.04120(9) 0.1199(7) Uani 1 1 d . . . F5 F 0.46261(16) 0.35247(13) 0.01835(8) 0.0974(5) Uani 1 1 d . . . F6 F 0.41406(19) 0.14164(13) -0.00405(7) 0.1060(6) Uani 1 1 d . . . F7 F 0.2401(2) 0.00299(15) -0.04696(9) 0.1291(7) Uani 1 1 d . . . F8 F 0.09828(18) -0.07685(13) 0.03408(10) 0.1140(6) Uani 1 1 d . . . F9 F 0.13460(16) -0.01008(12) 0.16015(9) 0.1018(6) Uani 1 1 d . . . F10 F 0.30877(14) 0.13069(11) 0.20449(7) 0.0783(4) Uani 1 1 d . . . F11 F 0.60780(15) 0.38371(11) 0.21582(8) 0.0927(5) Uani 1 1 d . . . F12 F 0.5065(2) 0.55520(12) 0.23322(10) 0.1180(7) Uani 1 1 d . . . F13 F 0.2454(2) 0.59707(12) 0.17223(9) 0.1090(6) Uani 1 1 d . . . F14 F 0.09476(17) 0.46508(12) 0.09473(9) 0.1047(6) Uani 1 1 d . . . F15 F 0.19268(14) 0.29373(11) 0.07661(8) 0.0855(5) Uani 1 1 d . . . C1 C 0.5961(2) 0.24744(16) 0.09630(11) 0.0528(6) Uani 1 1 d . . . C2 C 0.7222(2) 0.20666(17) 0.11535(12) 0.0593(6) Uani 1 1 d . . . C3 C 0.8237(2) 0.2234(2) 0.08478(15) 0.0717(7) Uani 1 1 d . . . C4 C 0.8032(3) 0.2845(2) 0.03215(16) 0.0781(8) Uani 1 1 d . . . C5 C 0.6812(3) 0.3284(2) 0.01097(13) 0.0761(8) Uani 1 1 d . . . C6 C 0.5822(3) 0.30871(19) 0.04312(12) 0.0649(7) Uani 1 1 d . . . C7 C 0.3726(2) 0.14309(16) 0.10334(11) 0.0525(6) Uani 1 1 d . . . C8 C 0.3481(3) 0.10598(19) 0.03990(13) 0.0678(7) Uani 1 1 d . . . C9 C 0.2572(3) 0.0343(2) 0.01573(14) 0.0793(8) Uani 1 1 d . . . C10 C 0.1850(3) -0.0048(2) 0.05618(16) 0.0783(8) Uani 1 1 d . . . C11 C 0.2037(3) 0.02874(19) 0.11962(15) 0.0682(7) Uani 1 1 d . . . C12 C 0.2949(2) 0.10033(17) 0.14082(12) 0.0577(6) Uani 1 1 d . . . C13 C 0.4063(2) 0.32910(16) 0.14601(11) 0.0520(6) Uani 1 1 d . . . C14 C 0.4775(2) 0.40049(19) 0.18491(13) 0.0647(7) Uani 1 1 d . . . C15 C 0.4288(3) 0.4896(2) 0.19522(14) 0.0748(8) Uani 1 1 d . . . C16 C 0.2995(4) 0.51038(19) 0.16471(15) 0.0758(8) Uani 1 1 d . . . C17 C 0.2231(3) 0.4437(2) 0.12566(14) 0.0692(7) Uani 1 1 d . . . C18 C 0.2760(2) 0.35535(18) 0.11695(12) 0.0587(6) Uani 1 1 d . . . N1 N 0.5742(2) 0.09589(17) 0.30454(12) 0.0632(6) Uani 1 1 d . . . H1A H 0.500(3) 0.078(2) 0.3130(14) 0.089(10) Uiso 1 1 d . . . H1B H 0.549(3) 0.130(2) 0.2661(15) 0.087(10) Uiso 1 1 d . . . C19 C 0.6387(3) 0.1683(2) 0.35847(13) 0.0802(8) Uani 1 1 d . . . C20 C 0.5355(4) 0.2489(3) 0.35316(18) 0.1152(12) Uani 1 1 d . . . H20A H 0.5698 0.2973 0.3859 0.173 Uiso 1 1 calc R . . H20B H 0.4539 0.2231 0.3607 0.173 Uiso 1 1 calc R . . H20C H 0.5181 0.2769 0.3096 0.173 Uiso 1 1 calc R . . C21 C 0.6650(4) 0.1185(3) 0.42536(14) 0.1265(15) Uani 1 1 d . . . H21A H 0.7055 0.1630 0.4597 0.190 Uiso 1 1 calc R . . H21B H 0.7242 0.0651 0.4257 0.190 Uiso 1 1 calc R . . H21C H 0.5819 0.0958 0.4330 0.190 Uiso 1 1 calc R . . C22 C 0.7671(3) 0.2041(3) 0.34282(16) 0.1075(12) Uani 1 1 d . . . H22A H 0.8096 0.2497 0.3760 0.161 Uiso 1 1 calc R . . H22B H 0.7464 0.2344 0.3000 0.161 Uiso 1 1 calc R . . H22C H 0.8263 0.1509 0.3426 0.161 Uiso 1 1 calc R . . C23 C 0.6529(3) 0.0098(2) 0.29355(16) 0.0882(9) Uani 1 1 d . . . H23A H 0.7248 0.0298 0.2738 0.106 Uiso 1 1 calc R . . H23B H 0.6926 -0.0202 0.3359 0.106 Uiso 1 1 calc R . . C24 C 0.5664(2) -0.06144(18) 0.24905(15) 0.0665(7) Uani 1 1 d . . . C25 C 0.5539(3) -0.0607(2) 0.18125(16) 0.0760(8) Uani 1 1 d . . . H25A H 0.6017 -0.0163 0.1627 0.091 Uiso 1 1 calc R . . C26 C 0.4706(3) -0.1257(2) 0.14098(15) 0.0824(8) Uani 1 1 d . . . H26A H 0.4625 -0.1246 0.0954 0.099 Uiso 1 1 calc R . . C27 C 0.4003(3) -0.1913(2) 0.16725(19) 0.0950(10) Uani 1 1 d . . . H27A H 0.3439 -0.2345 0.1397 0.114 Uiso 1 1 calc R . . C28 C 0.4128(4) -0.1935(2) 0.2337(2) 0.1031(11) Uani 1 1 d . . . H28A H 0.3653 -0.2388 0.2517 0.124 Uiso 1 1 calc R . . C29 C 0.4947(3) -0.1296(2) 0.27462(16) 0.0865(9) Uani 1 1 d . . . H29A H 0.5023 -0.1321 0.3202 0.104 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 B1 0.0497(15) 0.0609(17) 0.0462(15) 0.0046(13) 0.0116(12) 0.0037(13) F1 0.0726(10) 0.0946(11) 0.0909(11) 0.0210(9) 0.0177(8) 0.0256(8) F2 0.0555(10) 0.1446(16) 0.1339(15) -0.0188(13) 0.0268(10) 0.0162(10) F3 0.0968(13) 0.1579(17) 0.1298(15) -0.0221(13) 0.0716(12) -0.0395(12) F4 0.1486(17) 0.1306(16) 0.0974(13) 0.0385(12) 0.0624(12) -0.0050(13) F5 0.0868(11) 0.1280(14) 0.0807(11) 0.0418(10) 0.0269(9) 0.0308(10) F6 0.1348(15) 0.1277(14) 0.0651(10) -0.0188(10) 0.0432(10) -0.0465(12) F7 0.1678(19) 0.1335(16) 0.0854(13) -0.0464(12) 0.0298(12) -0.0490(14) F8 0.1095(14) 0.0878(12) 0.1371(16) -0.0253(11) 0.0154(12) -0.0378(11) F9 0.0894(12) 0.1040(13) 0.1222(14) 0.0039(11) 0.0453(11) -0.0306(10) F10 0.0758(10) 0.1003(11) 0.0674(9) -0.0068(8) 0.0339(8) -0.0156(8) F11 0.0662(10) 0.0918(11) 0.1111(13) -0.0169(10) 0.0040(9) -0.0189(8) F12 0.1413(16) 0.0812(12) 0.1351(16) -0.0421(11) 0.0402(13) -0.0356(11) F13 0.1547(17) 0.0687(11) 0.1271(14) 0.0008(10) 0.0798(13) 0.0240(11) F14 0.0812(12) 0.1002(12) 0.1349(15) 0.0264(11) 0.0308(11) 0.0351(10) F15 0.0633(9) 0.0811(10) 0.0977(12) -0.0014(9) -0.0086(8) 0.0062(8) C1 0.0496(14) 0.0556(14) 0.0529(14) -0.0014(11) 0.0118(11) -0.0016(11) C2 0.0569(15) 0.0625(15) 0.0591(15) -0.0018(13) 0.0149(12) 0.0017(12) C3 0.0492(16) 0.0847(19) 0.082(2) -0.0195(16) 0.0186(14) -0.0021(14) C4 0.0681(19) 0.094(2) 0.083(2) -0.0165(18) 0.0386(16) -0.0218(17) C5 0.093(2) 0.0804(19) 0.0614(17) 0.0069(15) 0.0322(16) -0.0109(16) C6 0.0626(16) 0.0733(17) 0.0611(16) 0.0090(14) 0.0199(13) 0.0062(13) C7 0.0494(13) 0.0543(14) 0.0536(14) 0.0021(11) 0.0125(11) 0.0058(11) C8 0.0773(18) 0.0707(17) 0.0597(16) -0.0035(14) 0.0253(14) -0.0087(14) C9 0.091(2) 0.0762(19) 0.0675(19) -0.0200(16) 0.0132(16) -0.0096(16) C10 0.0709(18) 0.0640(18) 0.096(2) -0.0100(17) 0.0115(17) -0.0124(15) C11 0.0581(16) 0.0653(16) 0.084(2) 0.0052(15) 0.0235(14) -0.0047(13) C12 0.0537(14) 0.0621(15) 0.0583(15) 0.0001(12) 0.0156(12) 0.0037(12) C13 0.0475(13) 0.0599(14) 0.0523(13) 0.0016(11) 0.0193(11) -0.0041(11) C14 0.0567(16) 0.0703(18) 0.0710(17) -0.0042(14) 0.0227(14) -0.0102(13) C15 0.091(2) 0.0613(18) 0.0805(19) -0.0141(15) 0.0372(17) -0.0169(17) C16 0.102(2) 0.0554(17) 0.087(2) 0.0018(15) 0.0564(19) 0.0070(17) C17 0.0631(17) 0.0731(19) 0.0804(19) 0.0164(16) 0.0348(15) 0.0148(15) C18 0.0568(15) 0.0606(15) 0.0605(15) 0.0013(13) 0.0180(13) -0.0018(13) N1 0.0552(14) 0.0709(15) 0.0599(14) -0.0016(12) 0.0069(12) -0.0063(12) C19 0.0757(18) 0.102(2) 0.0618(17) -0.0166(16) 0.0141(14) -0.0384(17) C20 0.124(3) 0.110(3) 0.119(3) -0.054(2) 0.045(2) -0.024(2) C21 0.126(3) 0.187(4) 0.0584(19) -0.001(2) 0.0069(19) -0.065(3) C22 0.096(2) 0.128(3) 0.103(2) -0.026(2) 0.0333(19) -0.060(2) C23 0.0637(18) 0.081(2) 0.111(2) 0.0031(18) 0.0045(17) 0.0107(16) C24 0.0633(16) 0.0561(16) 0.081(2) 0.0065(14) 0.0191(14) 0.0128(13) C25 0.0735(19) 0.0651(18) 0.097(2) 0.0164(17) 0.0358(17) 0.0138(14) C26 0.097(2) 0.078(2) 0.0761(19) -0.0049(17) 0.0294(18) 0.0236(18) C27 0.107(2) 0.070(2) 0.112(3) -0.0211(19) 0.035(2) -0.0010(18) C28 0.132(3) 0.072(2) 0.123(3) -0.011(2) 0.066(3) -0.026(2) C29 0.118(3) 0.0705(19) 0.080(2) 0.0043(17) 0.0406(19) 0.0048(18) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag B1 C7 1.632(3) . ? B1 C1 1.634(3) . ? B1 C13 1.638(3) . ? F1 C2 1.348(3) . ? F2 C3 1.345(3) . ? F3 C4 1.346(3) . ? F4 C5 1.341(3) . ? F5 C6 1.357(3) . ? F6 C8 1.356(3) . ? F7 C9 1.342(3) . ? F8 C10 1.346(3) . ? F9 C11 1.339(3) . ? F10 C12 1.361(3) . ? F11 C14 1.359(3) . ? F12 C15 1.337(3) . ? F13 C16 1.353(3) . ? F14 C17 1.355(3) . ? F15 C18 1.350(3) . ? C1 C6 1.374(3) . ? C1 C2 1.383(3) . ? C2 C3 1.368(3) . ? C3 C4 1.359(4) . ? C4 C5 1.370(4) . ? C5 C6 1.375(4) . ? C7 C12 1.378(3) . ? C7 C8 1.379(3) . ? C8 C9 1.377(4) . ? C9 C10 1.362(4) . ? C10 C11 1.365(4) . ? C11 C12 1.367(3) . ? C13 C14 1.374(3) . ? C13 C18 1.379(3) . ? C14 C15 1.373(4) . ? C15 C16 1.359(4) . ? C16 C17 1.352(4) . ? C17 C18 1.373(3) . ? N1 C23 1.494(3) . ? N1 C19 1.532(3) . ? C19 C21 1.516(4) . ? C19 C22 1.519(4) . ? C19 C20 1.530(4) . ? C23 C24 1.493(4) . ? C24 C25 1.381(4) . ? C24 C29 1.384(4) . ? C25 C26 1.380(4) . ? C26 C27 1.358(4) . ? C27 C28 1.353(4) . ? C28 C29 1.370(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C7 B1 C1 114.89(19) . . ? C7 B1 C13 113.18(19) . . ? C1 B1 C13 109.57(19) . . ? C6 C1 C2 113.1(2) . . ? C6 C1 B1 124.0(2) . . ? C2 C1 B1 122.9(2) . . ? F1 C2 C3 115.9(2) . . ? F1 C2 C1 119.5(2) . . ? C3 C2 C1 124.6(2) . . ? F2 C3 C4 119.6(3) . . ? F2 C3 C2 120.9(3) . . ? C4 C3 C2 119.5(3) . . ? F3 C4 C3 121.3(3) . . ? F3 C4 C5 119.5(3) . . ? C3 C4 C5 119.2(2) . . ? F4 C5 C4 120.0(3) . . ? F4 C5 C6 121.0(3) . . ? C4 C5 C6 119.0(3) . . ? F5 C6 C1 119.4(2) . . ? F5 C6 C5 116.0(2) . . ? C1 C6 C5 124.7(2) . . ? C12 C7 C8 112.4(2) . . ? C12 C7 B1 120.2(2) . . ? C8 C7 B1 127.5(2) . . ? F6 C8 C9 115.3(2) . . ? F6 C8 C7 120.0(2) . . ? C9 C8 C7 124.7(2) . . ? F7 C9 C10 120.3(3) . . ? F7 C9 C8 120.4(3) . . ? C10 C9 C8 119.3(2) . . ? F8 C10 C9 120.2(3) . . ? F8 C10 C11 120.6(3) . . ? C9 C10 C11 119.1(2) . . ? F9 C11 C10 119.7(2) . . ? F9 C11 C12 121.3(3) . . ? C10 C11 C12 119.0(2) . . ? F10 C12 C11 116.2(2) . . ? F10 C12 C7 118.4(2) . . ? C11 C12 C7 125.5(2) . . ? C14 C13 C18 112.9(2) . . ? C14 C13 B1 120.4(2) . . ? C18 C13 B1 126.6(2) . . ? F11 C14 C15 115.9(2) . . ? F11 C14 C13 118.6(2) . . ? C15 C14 C13 125.5(2) . . ? F12 C15 C16 120.5(3) . . ? F12 C15 C14 121.3(3) . . ? C16 C15 C14 118.2(3) . . ? C17 C16 F13 119.0(3) . . ? C17 C16 C15 119.6(2) . . ? F13 C16 C15 121.3(3) . . ? C16 C17 F14 119.4(3) . . ? C16 C17 C18 120.1(3) . . ? F14 C17 C18 120.4(3) . . ? F15 C18 C17 115.9(2) . . ? F15 C18 C13 120.5(2) . . ? C17 C18 C13 123.6(2) . . ? C23 N1 C19 118.9(2) . . ? C21 C19 C22 112.0(3) . . ? C21 C19 C20 111.6(3) . . ? C22 C19 C20 111.6(3) . . ? C21 C19 N1 108.5(3) . . ? C22 C19 N1 107.8(2) . . ? C20 C19 N1 105.0(2) . . ? C24 C23 N1 111.3(2) . . ? C25 C24 C29 117.9(3) . . ? C25 C24 C23 121.3(3) . . ? C29 C24 C23 120.8(3) . . ? C26 C25 C24 120.2(3) . . ? C27 C26 C25 120.7(3) . . ? C28 C27 C26 119.8(3) . . ? C27 C28 C29 120.6(3) . . ? C28 C29 C24 120.8(3) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.145 _refine_diff_density_min -0.216 _refine_diff_density_rms 0.041 #===end #===end