Achiral CpxIr(III)/Chiral Carboxylic Acid Catalyzed Enantioselective C‒H Amidation of Ferrocenes under Mild Conditions
Liu, Lei; Song, Hong; Liu, Yan-Hua; Wu, Le-Song; Shi, Bing-Feng; ACS Catalysis 10 (2020) 7117–7122; doi:10.1021/acscatal.0c02049

data_4517773
_publ_section_title
;
 Achiral CpxIr(III)/Chiral Carboxylic Acid Catalyzed Enantioselective C--H
 Amidation of Ferrocenes under Mild Conditions
;
_journal_issue                   13
_journal_name_full               'ACS Catalysis'
_journal_page_first              7117
_journal_page_last               7122
_journal_paper_doi               10.1021/acscatal.0c02049
_journal_volume                  10
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H18 Br2 Fe N2 O2'
_chemical_formula_sum            'C20 H18 Br2 Fe N2 O2'
_chemical_formula_weight         534.03
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5631(3)
_cell_length_b                   10.5631(3)
_cell_length_c                   34.9612(11)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      25.43
_cell_measurement_theta_min      2.33
_cell_volume                     3900.9(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0567
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            47114
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.417
_diffrn_reflns_theta_min         2.330
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.888
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5180
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1037 before and 0.0733 after correction.
The Ratio of minimum to maximum transmission is 0.6949.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.819
_exptl_crystal_description       block
_exptl_crystal_F_000             2112
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.748
_refine_diff_density_min         -0.782
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 1261 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         4020
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0093P)^2^+6.8702P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0797
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.666
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3529
_reflns_number_total             4020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02049_si_003.cif
_cod_data_source_block           191127_ll_4_122_3_0m
_cod_depositor_comments
;Adding full bibliography for 4517772--4517773.cif.

 Adding full bibliography for 4517772--4517773.cif.
;
_cod_original_cell_volume        3900.9(3)
_cod_database_code               4517773
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.667
_shelx_estimated_absorpt_t_min   0.569
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
3.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10),
 C13(H13), C15(H15), C17(H17)
3.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              2517
_shelx_hkl_checksum              56734
_olex2_submission_special_instructions 'No special instructions were received'