Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_k0210 _database_code_CSD 192434 _journal_coden_Cambridge 182 loop_ _publ_author_name 'Dmitry G. Gusev' 'Vladimir F. Kuznetsov' 'Alan Lough' _publ_contact_author_name 'Prof Dmitry G. Gusev' _publ_contact_author_address ; Department of Chemistry Wilfrid Laurier University 75 University Avenue West Waterloo Ontario N2L 3C5 CANADA ; _publ_contact_author_email 'DGOUSSEV@WLU.CA' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Triple C-H activation of 1,5-bis(di-tert-butylphosphino)-2-(S)-dimethylaminopentane on ruthenium gives a chiral carbene complex. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C23 H48 Cl N P2 Ru' _chemical_formula_weight 537.08 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' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ru' 'Ru' -1.2594 0.8363 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 8.4390(2) _cell_length_b 14.5810(4) _cell_length_c 21.9890(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2705.73(12) _cell_formula_units_Z 4 _cell_measurement_temperature 150(1) _cell_measurement_reflns_used 21905 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 27.48 _exptl_crystal_description 'needle' _exptl_crystal_colour 'red' _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.318 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1136 _exptl_absorpt_coefficient_mu 0.806 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.919 _exptl_absorpt_correction_T_max 0.969 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa-CCD' _diffrn_measurement_method '\f scans and \w scans from \k offsets' _diffrn_detector_area_resol_mean 9 _diffrn_standards_number 'none' _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 'none' _diffrn_reflns_number 21334 _diffrn_reflns_av_R_equivalents 0.0768 _diffrn_reflns_av_sigmaI/netI 0.0860 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6188 _reflns_number_gt 4637 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius BV, 1997-2001)' _computing_cell_refinement 'Denzo-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'Denzo-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXTL V6.12 (Sheldrick 2001)' _computing_structure_refinement 'SHELXTL V6.12 (Sheldrick 2001)' _computing_molecular_graphics 'SHELXTL V6.12 (Sheldrick 2001)' _computing_publication_material 'SHELXTL V6.12 (Sheldrick 2001)' _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^)+(0.0167P)^2^] 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 SHELXL _refine_ls_extinction_coef 0.0022(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.03(4) _refine_ls_number_reflns 6188 _refine_ls_number_parameters 267 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0696 _refine_ls_R_factor_gt 0.0405 _refine_ls_wR_factor_ref 0.0840 _refine_ls_wR_factor_gt 0.0745 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0.001 _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 Ru1 Ru 0.49751(4) 0.484436(18) 0.512944(11) 0.01974(9) Uani 1 1 d . . . Cl1 Cl 0.22594(12) 0.42738(8) 0.49586(5) 0.0356(3) Uani 1 1 d . . . P1 P 0.50225(16) 0.46570(6) 0.61824(4) 0.0229(2) Uani 1 1 d . . . P2 P 0.53516(12) 0.55026(7) 0.41673(4) 0.0240(3) Uani 1 1 d . . . N1 N 0.7787(4) 0.3899(2) 0.53951(14) 0.0231(8) Uani 1 1 d . . . C1 C 0.7186(5) 0.4719(3) 0.63355(16) 0.0278(10) Uani 1 1 d . . . H1A H 0.7435 0.5269 0.6582 0.033 Uiso 1 1 calc R . . H1B H 0.7538 0.4169 0.6562 0.033 Uiso 1 1 calc R . . C2 C 0.8023(4) 0.4771(3) 0.57173(16) 0.0235(9) Uani 1 1 d . . . H2A H 0.9176 0.4910 0.5767 0.028 Uiso 1 1 calc R . . C3 C 0.7206(5) 0.5492(3) 0.53080(17) 0.0262(9) Uani 1 1 d . . . H3A H 0.7037 0.6073 0.5541 0.031 Uiso 1 1 calc R . . C4 C 0.8203(5) 0.5682(3) 0.47428(17) 0.0284(10) Uani 1 1 d . . . H4A H 0.9117 0.6074 0.4854 0.034 Uiso 1 1 calc R . . H4B H 0.8620 0.5097 0.4580 0.034 Uiso 1 1 calc R . . C5 C 0.7218(5) 0.6161(3) 0.42556(18) 0.0316(10) Uani 1 1 d . . . H5A H 0.7804 0.6176 0.3866 0.038 Uiso 1 1 calc R . . H5B H 0.6983 0.6799 0.4380 0.038 Uiso 1 1 calc R . . C6 C 0.8865(5) 0.3122(3) 0.5491(2) 0.0317(10) Uani 1 1 d . . . H6A H 0.8436 0.2576 0.5290 0.048 Uiso 1 1 calc R . . H6B H 0.8972 0.3004 0.5928 0.048 Uiso 1 1 calc R . . H6C H 0.9907 0.3267 0.5319 0.048 Uiso 1 1 calc R . . C7 C 0.6428(4) 0.3879(3) 0.51005(17) 0.0232(9) Uani 1 1 d . . . H7A H 0.6178 0.3354 0.4864 0.028 Uiso 1 1 calc R . . C8 C 0.4402(5) 0.3544(3) 0.65673(18) 0.0281(10) Uani 1 1 d . . . C9 C 0.2586(6) 0.3499(3) 0.6607(2) 0.0446(13) Uani 1 1 d . . . H9A H 0.2260 0.2876 0.6717 0.067 Uiso 1 1 calc R . . H9B H 0.2127 0.3662 0.6212 0.067 Uiso 1 1 calc R . . H9C H 0.2213 0.3931 0.6917 0.067 Uiso 1 1 calc R . . C10 C 0.4952(7) 0.2751(2) 0.61583(17) 0.0373(10) Uani 1 1 d . . . H10A H 0.4678 0.2165 0.6350 0.056 Uiso 1 1 calc R . . H10B H 0.6103 0.2786 0.6102 0.056 Uiso 1 1 calc R . . H10C H 0.4427 0.2795 0.5762 0.056 Uiso 1 1 calc R . . C11 C 0.5093(8) 0.3380(3) 0.72035(16) 0.0450(11) Uani 1 1 d . . . H11A H 0.4680 0.2802 0.7367 0.068 Uiso 1 1 calc R . . H11B H 0.4789 0.3886 0.7472 0.068 Uiso 1 1 calc R . . H11C H 0.6251 0.3347 0.7177 0.068 Uiso 1 1 calc R . . C12 C 0.4096(5) 0.5646(3) 0.66061(17) 0.0286(10) Uani 1 1 d . . . C13 C 0.4264(6) 0.5600(4) 0.73031(17) 0.0433(12) Uani 1 1 d . . . H13A H 0.3872 0.6171 0.7483 0.065 Uiso 1 1 calc R . . H13B H 0.5382 0.5516 0.7410 0.065 Uiso 1 1 calc R . . H13C H 0.3645 0.5082 0.7459 0.065 Uiso 1 1 calc R . . C14 C 0.2326(5) 0.5725(4) 0.6439(2) 0.0443(13) Uani 1 1 d . . . H14A H 0.1899 0.6300 0.6602 0.066 Uiso 1 1 calc R . . H14B H 0.1745 0.5207 0.6614 0.066 Uiso 1 1 calc R . . H14C H 0.2209 0.5719 0.5996 0.066 Uiso 1 1 calc R . . C15 C 0.4863(7) 0.6545(3) 0.63903(18) 0.0387(11) Uani 1 1 d . . . H15A H 0.4383 0.7063 0.6607 0.058 Uiso 1 1 calc R . . H15B H 0.4693 0.6618 0.5952 0.058 Uiso 1 1 calc R . . H15C H 0.6003 0.6528 0.6475 0.058 Uiso 1 1 calc R . . C16 C 0.5651(5) 0.4780(3) 0.34661(17) 0.0316(10) Uani 1 1 d . . . C17 C 0.7251(6) 0.4295(3) 0.35261(19) 0.0389(12) Uani 1 1 d . . . H17A H 0.7398 0.3876 0.3182 0.058 Uiso 1 1 calc R . . H17B H 0.7277 0.3947 0.3907 0.058 Uiso 1 1 calc R . . H17C H 0.8102 0.4752 0.3527 0.058 Uiso 1 1 calc R . . C18 C 0.4343(6) 0.4040(3) 0.34498(19) 0.0401(12) Uani 1 1 d . . . H18A H 0.4548 0.3615 0.3113 0.060 Uiso 1 1 calc R . . H18B H 0.3310 0.4334 0.3391 0.060 Uiso 1 1 calc R . . H18C H 0.4342 0.3701 0.3835 0.060 Uiso 1 1 calc R . . C19 C 0.5654(6) 0.5316(4) 0.28647(17) 0.0441(13) Uani 1 1 d . . . H19A H 0.5902 0.4899 0.2529 0.066 Uiso 1 1 calc R . . H19B H 0.6455 0.5802 0.2883 0.066 Uiso 1 1 calc R . . H19C H 0.4608 0.5590 0.2799 0.066 Uiso 1 1 calc R . . C20 C 0.3821(5) 0.6415(3) 0.4021(2) 0.0315(10) Uani 1 1 d . . . C21 C 0.2291(5) 0.6013(3) 0.3774(2) 0.0381(11) Uani 1 1 d . . . H21A H 0.1456 0.6480 0.3785 0.057 Uiso 1 1 calc R . . H21B H 0.1975 0.5487 0.4023 0.057 Uiso 1 1 calc R . . H21C H 0.2456 0.5813 0.3353 0.057 Uiso 1 1 calc R . . C22 C 0.4374(6) 0.7202(3) 0.3614(2) 0.0431(13) Uani 1 1 d . . . H22A H 0.3539 0.7667 0.3589 0.065 Uiso 1 1 calc R . . H22B H 0.4604 0.6965 0.3206 0.065 Uiso 1 1 calc R . . H22C H 0.5335 0.7476 0.3786 0.065 Uiso 1 1 calc R . . C23 C 0.3446(6) 0.6803(3) 0.4657(2) 0.0379(12) Uani 1 1 d . . . H23A H 0.2683 0.7306 0.4620 0.057 Uiso 1 1 calc R . . H23B H 0.4423 0.7031 0.4844 0.057 Uiso 1 1 calc R . . H23C H 0.2994 0.6317 0.4912 0.057 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 Ru1 0.01757(14) 0.02010(14) 0.02155(14) 0.00095(12) 0.00021(17) -0.00100(19) Cl1 0.0212(5) 0.0447(7) 0.0409(6) 0.0052(5) -0.0031(4) -0.0089(5) P1 0.0237(5) 0.0222(5) 0.0227(4) -0.0004(3) -0.0009(6) -0.0007(7) P2 0.0262(7) 0.0222(5) 0.0238(5) 0.0030(4) 0.0014(4) 0.0013(4) N1 0.0172(19) 0.0210(19) 0.0310(19) 0.0026(15) 0.0012(14) -0.0012(15) C1 0.033(2) 0.026(2) 0.024(2) 0.0022(18) -0.0041(17) -0.006(2) C2 0.0186(19) 0.021(2) 0.031(2) 0.0015(18) -0.0024(16) -0.0027(18) C3 0.028(2) 0.019(2) 0.032(2) -0.0001(17) 0.0032(18) 0.0006(18) C4 0.021(2) 0.028(2) 0.036(2) 0.004(2) -0.0001(17) -0.0092(18) C5 0.032(3) 0.027(3) 0.036(2) 0.0052(19) 0.005(2) -0.004(2) C6 0.024(2) 0.025(2) 0.046(3) 0.007(2) -0.001(2) 0.0042(19) C7 0.023(2) 0.021(2) 0.025(2) -0.0006(18) 0.0023(18) -0.0086(16) C8 0.027(2) 0.029(2) 0.028(2) 0.0036(19) 0.0019(17) -0.0027(18) C9 0.038(3) 0.039(3) 0.056(3) 0.007(2) 0.006(2) -0.006(2) C10 0.047(3) 0.022(2) 0.043(2) 0.0003(16) 0.012(3) -0.008(3) C11 0.067(3) 0.038(2) 0.030(2) 0.0082(17) -0.001(3) 0.001(4) C12 0.031(2) 0.027(2) 0.028(2) -0.0008(19) 0.0013(18) -0.001(2) C13 0.063(3) 0.040(3) 0.026(2) -0.005(2) 0.007(2) 0.005(3) C14 0.041(3) 0.040(3) 0.052(3) -0.008(2) 0.004(2) 0.007(3) C15 0.045(3) 0.031(2) 0.040(2) -0.0028(17) 0.008(3) 0.001(3) C16 0.039(2) 0.030(2) 0.025(2) 0.001(2) 0.0006(17) 0.011(2) C17 0.048(3) 0.036(3) 0.033(2) -0.004(2) 0.011(2) 0.010(2) C18 0.053(3) 0.037(3) 0.030(2) -0.007(2) -0.001(2) -0.003(2) C19 0.055(3) 0.053(3) 0.024(2) 0.007(2) 0.006(2) 0.005(3) C20 0.029(2) 0.029(3) 0.037(3) 0.004(2) -0.002(2) 0.003(2) C21 0.031(3) 0.040(3) 0.043(3) 0.004(2) -0.006(2) 0.008(2) C22 0.045(3) 0.033(3) 0.052(3) 0.019(2) 0.001(2) 0.008(2) C23 0.040(3) 0.032(3) 0.041(3) -0.006(2) 0.001(2) 0.009(2) _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 Ru1 C7 1.868(4) . ? Ru1 C3 2.143(4) . ? Ru1 P1 2.3317(9) . ? Ru1 P2 2.3448(10) . ? Ru1 Cl1 2.4668(10) . ? P1 C1 1.859(4) . ? P1 C12 1.887(4) . ? P1 C8 1.904(4) . ? P2 C5 1.854(4) . ? P2 C20 1.883(4) . ? P2 C16 1.885(4) . ? N1 C7 1.317(5) . ? N1 C6 1.468(5) . ? N1 C2 1.469(5) . ? C1 C2 1.534(5) . ? C2 C3 1.547(5) . ? C3 C4 1.526(5) . ? C4 C5 1.525(5) . ? C8 C11 1.534(5) . ? C8 C9 1.536(6) . ? C8 C10 1.537(5) . ? C12 C15 1.537(6) . ? C12 C13 1.541(5) . ? C12 C14 1.543(6) . ? C16 C17 1.530(6) . ? C16 C19 1.537(5) . ? C16 C18 1.543(6) . ? C20 C21 1.519(6) . ? C20 C22 1.528(6) . ? C20 C23 1.541(6) . ? 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 Ru1 C3 76.20(16) . . ? C7 Ru1 P1 86.24(12) . . ? C3 Ru1 P1 81.64(11) . . ? C7 Ru1 P2 100.87(12) . . ? C3 Ru1 P2 82.29(10) . . ? P1 Ru1 P2 160.31(4) . . ? C7 Ru1 Cl1 110.53(12) . . ? C3 Ru1 Cl1 173.16(11) . . ? P1 Ru1 Cl1 97.33(4) . . ? P2 Ru1 Cl1 97.27(4) . . ? C1 P1 C12 106.28(19) . . ? C1 P1 C8 103.37(19) . . ? C12 P1 C8 108.55(18) . . ? C1 P1 Ru1 101.02(12) . . ? C12 P1 Ru1 113.19(13) . . ? C8 P1 Ru1 122.45(13) . . ? C5 P2 C20 103.6(2) . . ? C5 P2 C16 105.1(2) . . ? C20 P2 C16 110.35(19) . . ? C5 P2 Ru1 103.44(13) . . ? C20 P2 Ru1 110.51(14) . . ? C16 P2 Ru1 121.82(15) . . ? C7 N1 C6 126.4(3) . . ? C7 N1 C2 112.0(3) . . ? C6 N1 C2 121.0(3) . . ? C2 C1 P1 107.1(2) . . ? N1 C2 C1 108.8(3) . . ? N1 C2 C3 104.3(3) . . ? C1 C2 C3 110.1(3) . . ? C4 C3 C2 110.6(3) . . ? C4 C3 Ru1 114.5(3) . . ? C2 C3 Ru1 101.4(2) . . ? C5 C4 C3 110.7(3) . . ? C4 C5 P2 107.5(3) . . ? N1 C7 Ru1 122.6(3) . . ? C11 C8 C9 108.7(4) . . ? C11 C8 C10 107.5(4) . . ? C9 C8 C10 107.6(4) . . ? C11 C8 P1 115.7(3) . . ? C9 C8 P1 109.6(3) . . ? C10 C8 P1 107.4(3) . . ? C15 C12 C13 107.8(4) . . ? C15 C12 C14 105.7(4) . . ? C13 C12 C14 109.2(3) . . ? C15 C12 P1 109.0(3) . . ? C13 C12 P1 114.8(3) . . ? C14 C12 P1 109.9(3) . . ? C17 C16 C19 107.9(3) . . ? C17 C16 C18 108.1(4) . . ? C19 C16 C18 109.7(3) . . ? C17 C16 P2 107.8(3) . . ? C19 C16 P2 114.8(3) . . ? C18 C16 P2 108.3(3) . . ? C21 C20 C22 109.8(4) . . ? C21 C20 C23 107.0(4) . . ? C22 C20 C23 108.6(4) . . ? C21 C20 P2 111.8(3) . . ? C22 C20 P2 114.9(3) . . ? C23 C20 P2 104.2(3) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.926 _refine_diff_density_min -0.630 _refine_diff_density_rms 0.098