N,O- vs N,C-Chelation in Half-Sandwich Iridium Complexes: A Dramatic Effect on Enantioselectivity in Asymmetric Transfer Hydrogenation of Ketones
Zhou, Gang; Aboo, Ahmed H.; Robertson, Craig M.; Liu, Ruixia; Li, Zhenhua; Luzyanin, Konstantin; Berry, Neil G.; Chen, Weiping; Xiao, Jianliang; ACS Catalysis 8 (2018) 8020–; doi:10.1021/acscatal.8b02068

data_4515742
_publ_section_title
;
 N,O- vs N,C-Chelation in Half-Sandwich Iridium Complexes: A Dramatic
 Effect on Enantioselectivity in Asymmetric Transfer Hydrogenation of
 Ketones
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              8020
_journal_paper_doi               10.1021/acscatal.8b02068
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H25 Cl Ir N O3'
_chemical_formula_sum            'C21 H25 Cl Ir N O3'
_chemical_formula_weight         567.07
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-04-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            6
_cell_length_a                   18.4094(18)
_cell_length_b                   18.4094(18)
_cell_length_c                   11.3169(7)
_cell_measurement_reflns_used    2402
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.36
_cell_measurement_theta_min      2.56
_cell_volume                     3321.5(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10858
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.38
_diffrn_reflns_theta_min         2.21
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.169
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.4331
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1090 before and 0.0613 after correction. The Ratio of minimum to maximum transmission is 0.5810. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.701
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1656
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.856
_refine_diff_density_min         -0.820
_refine_diff_density_rms         0.136
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.010(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4464
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0289
_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^)+(0.0204P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0670
_refine_ls_wR_factor_ref         0.0686
_reflns_number_gt                4096
_reflns_number_total             4464
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs8b02068_si_002.cif
_cod_data_source_block           mo_zg_ox_1_0m_a
_cod_database_code               4515742
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C2(H2), C4(H4), C3(H3)
2.d Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C17(H17a,H17b,H17c), C20(H20a,H20b,H20c), C19(H19a,H19b,
 H19c), C21(H21a,H21b,H21c), C11(H11a,H11b,H11c)
;
_olex2_submission_special_instructions 'No special instructions were received'