C2-Symmetric Atropisomeric N-Heterocyclic Carbene-Palladium(II) Complexes: Synthesis, Chiral Resolution and Application in enantioselective α-Arylation of Amides
Kong, Lingyu; Chou, Yajie; ALBALAT, Muriel; Jean, Marion; Vanthuyne, Nicolas; Nava, Paola; Humbel, Stéphane; Clavier, Hervé; Dalton Transactions  (2023) –; doi:10.1039/D3DT01182H

data_7713120
_publ_section_title
;
 C2-Symmetric Atropisomeric N-Heterocyclic Carbene-Palladium(II)
 Complexes: Synthesis, Chiral Resolution and Application in
 enantioselective \a-Arylation of Amides
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01182H
_journal_year                    2023
_chemical_formula_moiety         'C45 H39 F2 N2, B F4'
_chemical_formula_sum            'C45 H38 B F6 N2'
_chemical_formula_weight         731.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-02-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-20 deposited with the CCDC.	2023-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4939(14)
_cell_length_b                   17.6838(6)
_cell_length_c                   16.9141(11)
_cell_measurement_reflns_used    1829
_cell_measurement_temperature    295
_cell_measurement_theta_max      66.8010
_cell_measurement_theta_min      3.8730
_cell_volume                     4332.7(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.978
_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     68.00 103.00   1.00    2.50    --    0.00 178.00   0.00   35
  2  \w     36.00  91.00   1.00    2.50    --    0.00  57.00 -90.00   55
  3  \w     58.00  90.00   1.00    2.50    --    0.00 178.00 -90.00   32
  4  \w    -15.00  20.00   1.00    2.50    --    0.00  57.00 -90.00   35
  5  \w   -151.00 -80.00   1.00    2.50    --  -53.50 -94.00  30.00   71
  6  \w   -133.00 -82.00   1.00    2.50    --  -53.50 -94.00 120.00   51
  7  \w   -134.00 -86.00   1.00    2.50    --  -53.50 -94.00 -30.00   48
  8  \w    107.00 149.00   1.00    2.50    --   53.50 125.00  30.00   42
  9  \w     94.00 149.00   1.00    2.50    --   53.50 125.00-180.00   55
 10  \w     97.00 124.00   1.00    2.50    --   53.50 125.00 -30.00   27
 11  \w     95.00 149.00   1.00    2.50    --   53.50 125.00  90.00   54
 12  \w     61.00 174.00   1.00   45.00    --  107.00  38.00 -30.00  113
 13  \w    142.00 176.00   1.00   45.00    --  107.00  38.00 150.00   34
 14  \w     61.00  86.00   1.00   45.00    --  107.00  38.00 150.00   25
 15  \w    148.00 175.00   1.00   45.00    --  107.00  77.00 120.00   27
 16  \w     73.00 100.00   1.00   45.00    --  107.00  77.00 120.00   27
 17  \w    109.00 137.00   1.00   45.00    --  107.00 111.00 -30.00   28
 18  \w     12.00 153.00   1.00   45.00    --  107.00 -50.00 120.00  141
 19  \w     12.00  82.00   1.00   45.00    --  107.00-111.00 120.00   70
 20  \w     51.00 139.00   1.00   45.00    --  107.00 -63.00-150.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0493606000
_diffrn_orient_matrix_UB_12      -0.0634116000
_diffrn_orient_matrix_UB_13      0.0229570000
_diffrn_orient_matrix_UB_21      -0.0854441000
_diffrn_orient_matrix_UB_22      0.0090932000
_diffrn_orient_matrix_UB_23      -0.0932881000
_diffrn_orient_matrix_UB_31      0.0399032000
_diffrn_orient_matrix_UB_32      -0.0589756000
_diffrn_orient_matrix_UB_33      -0.0390167000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_av_unetI/netI     0.1139
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            14465
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.234
_diffrn_reflns_theta_min         3.051
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.687
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_description       plate
_exptl_crystal_F_000             1524
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7751
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1782
_refine_ls_R_factor_gt           0.0986
_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^)+(0.1498P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2795
_refine_ls_wR_factor_ref         0.3322
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3173
_reflns_number_total             7751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk4077diamaj
_cod_database_code               7713120
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c45 h33 b1 f6 n2'
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.820
_reflns_odcompleteness_completeness 99.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12), C32(H32)
2.b Aromatic/amide H refined with riding coordinates:
 C4AA(H4AA), C8(H8), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C28(H28), C30(H30),
  C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C25(H25A,H25B,H25C), C45(H45A,H45B,H45C)
;
_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.609