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_4515741
_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         'C20 H23 Cl Ir N O3, C H2 Cl2'
_chemical_formula_sum            'C21 H25 Cl3 Ir N O3'
_chemical_formula_weight         637.97
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.6875(10)
_cell_length_b                   13.7823(16)
_cell_length_c                   17.6769(18)
_cell_measurement_reflns_used    4227
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.61
_cell_measurement_theta_min      2.30
_cell_volume                     2360.1(4)
_computing_cell_refinement       'SAINT V8.30C (?, 2016)'
_computing_data_reduction        'SAINT V8.30C (?, 2016)'
_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      296.15
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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  0.0460
_diffrn_reflns_av_unetI/netI     0.0549
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            14625
_diffrn_reflns_theta_full        26.38
_diffrn_reflns_theta_max         26.38
_diffrn_reflns_theta_min         1.87
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.018
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.3968
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1601 before and 0.0607 after correction. The Ratio of minimum to maximum transmission is 0.5323. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.795
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1240
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.925
_refine_diff_density_min         -1.220
_refine_diff_density_rms         0.123
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.040(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         4786
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0378
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0452P)^2^+2.0443P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0988
_reflns_number_gt                3996
_reflns_number_total             4786
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs8b02068_si_003.cif
_cod_data_source_block           first_sb
_cod_database_code               4515741
_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. Uiso/Uaniso restraints and constraints
Cl3 \\sim C22 \\sim Cl2: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.005
3. Others
 Fixed U11: Cl3(0.08071) Cl2(0.08679) C22(0.0872)
4.a Ternary CH refined with riding coordinates:
 C9(H9)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C22(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C3(H3), C4(H4), C7(H7)
4.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C17(H17A,H17B,H17C)
;
_olex2_submission_special_instructions 'No special instructions were received'