Asymmetric synthesis of metallocenes with planar and central chirality by rhodium-catalyzed desymmetrization reactions.
Hang, Nan-Nan; Tong, En-Guang; Qi, Ting; Sun, Chao; Ming, Jialin; Chemical science 16 (2025) 5880–5886; doi:10.1039/d5sc00158g

data_1573989
_publ_section_title
;
 Asymmetric synthesis of metallocenes with planar and central chirality by
 rhodium-catalyzed desymmetrization reactions.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5880
_journal_page_last               5886
_journal_paper_doi               10.1039/d5sc00158g
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H15 Br Fe O2'
_chemical_formula_sum            'C18 H15 Br Fe O2'
_chemical_formula_weight         399.06
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-04-11
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-11-15 deposited with the CCDC.	2025-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                80.360(4)
_cell_angle_beta                 73.628(5)
_cell_angle_gamma                82.082(5)
_cell_formula_units_Z            2
_cell_length_a                   7.6130(5)
_cell_length_b                   8.5829(4)
_cell_length_c                   12.8193(7)
_cell_measurement_reflns_used    6293
_cell_measurement_temperature    219.99(10)
_cell_measurement_theta_max      73.2370
_cell_measurement_theta_min      3.5620
_cell_volume                     788.68(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      219.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -114.00 -59.00   1.00    1.30    --  -40.98 -37.00 150.00   55
  2  \w    -58.00 -20.00   1.00    1.30    --  -40.98 -37.00 150.00   38
  3  \w   -112.00 -13.00   1.00    1.30    --  -40.98 -57.00 -60.00   99
  4  \w    -63.00  31.00   1.00    1.30    --  -40.98  37.00 -60.00   94
  5  \w     24.00  81.00   1.00    1.30    --   40.98-125.00-180.00   57
  6  \w      1.00  81.00   1.00    1.30    --   40.98 -99.00  30.00   80
  7  \w     27.00  63.00   1.00    1.30    --   40.98-125.00   0.00   36
  8  \w     14.00  39.00   1.00    1.30    --   40.98  57.00   0.00   25
  9  \w      6.00  31.00   1.00    1.30    --   42.00  87.00 -61.95   25
 10  \w      6.00  33.00   1.00    1.30    --   42.00  88.00 110.54   27
 11  \w     11.00  38.00   1.00    1.30    --   46.00  84.00  23.98   27
 12  \w     20.00  45.00   1.00    1.30    --   50.00  81.00-172.02   25
 13  \w     20.00  46.00   1.00    1.30    --   54.00  81.00  75.40   26
 14  \w     21.00  46.00   1.00    1.30    --   54.00  79.00 -23.38   25
 15  \w     65.00 107.00   1.00    1.30    --   58.00  76.00 127.22   42
 16  \w     26.00  52.00   1.00    1.30    --   58.00  76.00 127.22   26
 17  \w     32.00  59.00   1.00    1.30    --   62.00  77.00 -15.17   27
 18  \w     29.00  61.00   1.00    1.30    --   62.00  77.00 140.59   32
 19  \w     30.00  79.00   1.00    1.30    --   62.00  77.00  33.99   49
 20  \w     85.00 136.00   1.00    1.30    --   62.00  77.00 -15.17   51
 21  \w     34.00  71.00   1.00    1.30    --   66.00  77.00 -67.12   37
 22  \w     35.00  66.00   1.00    1.30    --   66.00  76.00 156.69   31
 23  \w     90.00 142.00   1.00    1.30    --   66.00  77.00-151.98   52
 24  \w     34.00  70.00   1.00    1.30    --   66.00  77.00-151.98   36
 25  \w    113.00 146.00   1.00    1.30    --   70.00  77.00-103.11   33
 26  \w     37.00  72.00   1.00    1.30    --   70.00  77.00-103.11   35
 27  \w     76.00 178.00   1.00    2.60    --  107.58  77.00-150.00  102
 28  \w     82.00 131.00   1.00    2.60    --  107.58  61.00  30.00   49
 29  \w     79.00 131.00   1.00    2.60    --  107.58  77.00 150.00   52
 30  \w     75.00 146.00   1.00    2.60    --  107.58  77.00 -90.00   71
 31  \w     75.00 101.00   1.00    2.60    --  107.58  77.00 -30.00   26
 32  \w     78.00 104.00   1.00    2.60    --  107.58  61.00  60.00   26
 33  \w     81.00 108.00   1.00    2.60    --  107.58  61.00 150.00   27
 34  \w     80.00 176.00   1.00    2.60    --  107.58  61.00 -60.00   96
 35  \w     75.00 102.00   1.00    2.60    --  107.58  77.00   0.00   27
 36  \w    123.00 176.00   1.00    2.60    --  107.58  77.00 120.00   53
 37  \w     36.00 120.00   1.00    2.60    --  107.58-125.00  60.00   84
 38  \w     76.00 145.00   1.00    2.60    --  107.58  77.00  90.00   69
 39  \w     25.00 106.00   1.00    2.60    --  107.58 -94.00 150.00   81
 40  \w     76.00 177.00   1.00    2.60    --  107.58  77.00-180.00  101
 41  \w     78.00 105.00   1.00    2.60    --  107.58  61.00 -30.00   27
 42  \w     76.00 101.00   1.00    2.60    --  107.58  77.00 120.00   25
 43  \w    153.00 178.00   1.00    2.60    --  107.58  61.00  90.00   25
 44  \w     78.00 135.00   1.00    2.60    --  107.58  61.00-180.00   57
 45  \w    119.00 174.00   1.00    2.60    --  107.58  77.00  60.00   55
 46  \w     75.00 174.00   1.00    2.60    --  107.58  77.00  30.00   99
 47  \w     83.00 120.00   1.00    2.60    --  107.58  61.00  90.00   37
 48  \w     75.00 102.00   1.00    2.60    --  107.58  77.00  60.00   27
 49  \w    143.00 170.00   1.00    2.60    --  107.58  61.00   0.00   27
 50  \w     75.00 151.00   1.00    2.60    --  107.58  77.00-120.00   76
 51  \w     81.00 113.00   1.00    2.60    --  107.58  61.00   0.00   32
 52  \w    117.00 172.00   1.00    2.60    --  107.58  77.00 -30.00   55
 53  \w    140.00 178.00   1.00    2.60    --  107.58 125.00-150.00   38
 54  \w     41.00 133.00   1.00    2.60    --  107.58 -77.00-150.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0554608000
_diffrn_orient_matrix_UB_12      -0.1576470000
_diffrn_orient_matrix_UB_13      0.0715176000
_diffrn_orient_matrix_UB_21      -0.1276656000
_diffrn_orient_matrix_UB_22      0.0926571000
_diffrn_orient_matrix_UB_23      0.0901135000
_diffrn_orient_matrix_UB_31      -0.1597508000
_diffrn_orient_matrix_UB_32      0.0039082000
_diffrn_orient_matrix_UB_33      -0.0524035000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_av_unetI/netI     0.0644
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12506
_diffrn_reflns_point_group_measured_fraction_full 0.950
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.010
_diffrn_reflns_theta_min         3.627
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.660
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light red'
_exptl_crystal_density_diffrn    1.680
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.401
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2106 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         5856
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0484P)^2^+0.4043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1133
_refine_ls_wR_factor_ref         0.1195
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.904
_reflns_Friedel_fraction_max     0.850
_reflns_number_gt                5326
_reflns_number_total             5856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00158g2.cif
_cod_data_source_block           febr
_cod_depositor_comments          'Adding full bibliography for 1573989.cif.'
_cod_database_code               1573989
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C25(H25)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C23(H23),
  C24(H24), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36)
2.c Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3(H3A)
;
_shelx_res_checksum              4282
_olex2_date_sample_data_collection 2023-04-08
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.558
_oxdiff_exptl_absorpt_empirical_full_min 0.435