Chiral Bidentate Boryl Ligand-Enabled Iridium-Catalyzed Enantioselective Dual C–H Borylation of Ferrocenes: Reaction Development and Mechanistic Insights
Zou, Xiaoliang; Li, Yinwu; Ke, Zhuofeng; Xu, Senmiao; ACS Catalysis  (2022) 1830–1840; doi:10.1021/acscatal.1c05299

data_4519289
_publ_section_title
;
 Chiral Bidentate Boryl Ligand-Enabled Iridium-Catalyzed Enantioselective
 Dual C--H Borylation of Ferrocenes: Reaction Development and Mechanistic
 Insights
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1830
_journal_page_last               1840
_journal_paper_doi               10.1021/acscatal.1c05299
_journal_year                    2022
_chemical_formula_moiety         'C32 H40 B2 F3 Fe N O6'
_chemical_formula_sum            'C32 H40 B2 F3 Fe N O6'
_chemical_formula_weight         669.12
_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
_audit_creation_date             2019-12-20
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6087(2)
_cell_length_b                   12.4217(2)
_cell_length_c                   22.4749(4)
_cell_measurement_reflns_used    9837
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      68.23
_cell_measurement_theta_min      3.93
_cell_volume                     3240.88(10)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.02
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            42151
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         3.934
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.255
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1459 before and 0.0971 after correction.
The Ratio of minimum to maximum transmission is 0.5866.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.371
_exptl_crystal_description       block
_exptl_crystal_F_000             1400
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.998
_refine_diff_density_min         -0.596
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.035(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         5759
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0433P)^2^+4.8193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.734
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                5587
_reflns_number_total             5759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05299_si_002.cif
_cod_data_source_block           cu_20191219d_0ma_a
_cod_database_code               4519289
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.676
_shelx_estimated_absorpt_t_min   0.455
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.965(7)
 0.035(7)
2. 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
3.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7)
3.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              66072
_shelx_hkl_checksum              27970
_olex2_submission_special_instructions 'No special instructions were received'