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_7713121
_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         'B F4, C47 H45 N2'
_chemical_formula_sum            'C47 H45 B F4 N2'
_chemical_formula_weight         724.66
_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             2019-03-07
_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                 104.028(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4507(3)
_cell_length_b                   27.0470(8)
_cell_length_c                   16.5020(5)
_cell_measurement_reflns_used    4311
_cell_measurement_temperature    295
_cell_measurement_theta_max      69.9160
_cell_measurement_theta_min      4.2590
_cell_volume                     4092.3(2)
_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 0.997
_diffrn_measured_fraction_theta_max 0.982
_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    -71.00  32.00   1.00    5.00    --  -41.82  77.00  60.00  103
  2  \w    -83.00 -18.00   1.00    5.00    --  -41.82 -38.00-120.00   65
  3  \w    -56.00  20.00   1.00    5.00    --  -41.82  38.00   0.00   76
  4  \w   -104.00 -16.00   1.00    5.00    --  -41.82 -57.00-180.00   88
  5  \w     39.00 107.00   1.00   30.00    --  100.78-125.00 -90.00   68
  6  \w     25.00 123.00   1.00   30.00    --  100.78 -77.00  90.00   98
  7  \w     28.00 114.00   1.00   30.00    --  100.78 -45.00 -90.00   86
  8  \w     94.00 162.00   1.00   30.00    --  100.78  45.00  90.00   68
  9  \w     25.00 129.00   1.00   30.00    --  100.78 -30.00  60.00  104
 10  \w     40.00 117.00   1.00   30.00    --  100.78-125.00  90.00   77
 11  \w    104.00 150.00   1.00   30.00    --  100.78 125.00  30.00   46
 12  \w    104.00 130.00   1.00   30.00    --  100.78 125.00-150.00   26
 13  \w     51.00 107.00   1.00   30.00    --  100.78 -94.00 -60.00   56
 14  \w     17.00 118.00   1.00   30.00    --  100.78   0.00  60.00  101
;
_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      0.0736985000
_diffrn_orient_matrix_UB_12      -0.0221969000
_diffrn_orient_matrix_UB_13      0.0858286000
_diffrn_orient_matrix_UB_21      0.0432850000
_diffrn_orient_matrix_UB_22      0.0522807000
_diffrn_orient_matrix_UB_23      0.0342169000
_diffrn_orient_matrix_UB_31      -0.1446044000
_diffrn_orient_matrix_UB_32      0.0043420000
_diffrn_orient_matrix_UB_33      0.0269157000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0553
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            27064
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.660
_diffrn_reflns_theta_min         3.208
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92544
_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    1.176
_exptl_crystal_description       plate
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.247
_refine_diff_density_rms         0.034
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     529
_refine_ls_number_reflns         7721
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0663P)^2^+0.4004P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1441
_refine_ls_wR_factor_ref         0.1701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4936
_reflns_number_total             7721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk4082diamaj
_cod_database_code               7713121
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c45 h39 b1 f6 n2'
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.892
_reflns_odcompleteness_completeness 99.94
_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. Rigid body (RIGU) restrains
 F1, F2, F3, F4, B1, F8, F7, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: F1(0.8) F2(0.8) F3(0.8) F4(0.8) F5(0.2) F6(0.2) F7(0.2) F8(0.2)
4.a Ternary CH refined with riding coordinates:
 C14(H14), C35(H35)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C8(H8), C10(H10), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C29(H29), C31(H31), C37(H37),
  C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47)
4.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
;
_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 1.125
_oxdiff_exptl_absorpt_empirical_full_min 0.710