Catalytic Cycle for the Asymmetric Hydrogenation of Prochiral Ketones to Chiral Alcohols: Direct Hydride and Proton Transfer from Chiral Catalysts trans-Ru(H)2(diphosphine)(diamine) to Ketones and Direct Addition of Dihydrogen to the Resulting Hydridoamido Complexes
Kamaluddin Abdur-Rashid; Michael Faatz; Alan J. Lough; Robert H. Morris; Journal of the American Chemical Society 123 (2001) 7473–7474; doi:10.1021/ja015902u

data_4115632
_publ_section_title
;
 Catalytic Cycle for the Asymmetric Hydrogenation of Prochiral Ketones to
 Chiral Alcohols: Direct Hydride and Proton Transfer from Chiral Catalysts
 trans-Ru(H)2(diphosphine)(diamine) to Ketones and Direct Addition of
 Dihydrogen to the Resulting Hydridoamido Complexes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7473
_journal_page_last               7474
_journal_paper_doi               10.1021/ja015902u
_journal_volume                  123
_journal_year                    2001
_chemical_formula_sum            'C50 H49 Cl N2 P2 Ru'
_chemical_formula_weight         876.37
_chemical_name_common            RuHCl(R-binap)(tmen)
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           92
_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_Hall  'P 4abw 2nw'
_symmetry_space_group_name_H-M   'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   11.1960(8)
_cell_length_b                   11.1960(8)
_cell_length_c                   72.9290(18)
_cell_measurement_reflns_used    7437
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      25.03
_cell_measurement_theta_min      2.57
_cell_volume                     9141.7(10)
_computing_cell_refinement       'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction        'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL V5.1'
_computing_publication_material  'Bruker SHELXTL V5.1'
_computing_structure_refinement  'Bruker SHELXTL V5.1'
_computing_structure_solution    'Bruker SHELXTL V5.1'
_diffrn_ambient_temperature      150(1)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Nonius Kappa-CCD'
_diffrn_measurement_method       '\f scans and \w scans with \k offsets'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71070
_diffrn_reflns_av_R_equivalents  0.054
_diffrn_reflns_av_sigmaI/netI    0.0481
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       86
_diffrn_reflns_limit_l_min       -85
_diffrn_reflns_number            22637
_diffrn_reflns_theta_full        25.03
_diffrn_reflns_theta_max         25.03
_diffrn_reflns_theta_min         2.57
_diffrn_standards_decay_%        none
_exptl_absorpt_coefficient_mu    0.506
_exptl_absorpt_correction_T_max  0.8797
_exptl_absorpt_correction_T_min  0.8428
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Denzo-SMN (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.274
_exptl_crystal_F_000             3632
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.611
_refine_diff_density_min         -0.749
_refine_diff_density_rms         0.101
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.09(7)
_refine_ls_extinction_coef       0.0002(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.219
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         7437
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.219
_refine_ls_R_factor_all          0.0879
_refine_ls_R_factor_gt           0.0808
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+59.2433P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1749
_refine_ls_wR_factor_ref         0.1777
_reflns_number_gt                6826
_reflns_number_total             7437
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja015902u_s2_2.cif
_cod_data_source_block           complex3
_cod_original_formula_sum        'C50 H H48 Cl N2 P2 Ru'
_cod_database_code               4115632