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_7713126
_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_absolute_configuration ad
_chemical_formula_moiety         'C27 H35 Cl N2 Pd'
_chemical_formula_sum            'C27 H35 Cl N2 Pd'
_chemical_formula_weight         529.42
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-10-18
_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                70.3306(19)
_cell_angle_beta                 83.4315(17)
_cell_angle_gamma                80.1947(16)
_cell_formula_units_Z            2
_cell_length_a                   8.91439(18)
_cell_length_b                   11.5588(2)
_cell_length_c                   13.5263(3)
_cell_measurement_reflns_used    25403
_cell_measurement_temperature    293
_cell_measurement_theta_max      28.2850
_cell_measurement_theta_min      3.5310
_cell_volume                     1290.80(5)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.883
_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    -45.00  12.00   1.00   30.00    --   -7.86  89.00  55.00   57
  2  \w    -24.00  85.00   1.00   30.00    --    8.41  77.00 150.00  109
  3  \w    -16.00  83.00   1.00   30.00    --    8.41  38.00  90.00   99
  4  \w    -20.00  82.00   1.00   30.00    --    8.41  57.00 -90.00  102
  5  \w    -20.00  49.00   1.00   30.00    --    8.41 -99.00 -90.00   69
  6  \w    -15.00  53.00   1.00   30.00    --    8.41-105.00  -8.95   68
  7  \w    -65.00  42.00   1.00   30.00    --   10.00 -73.00 136.27  107
  8  \w    -20.00  33.00   1.00   30.00    --   -7.86 -99.00 -90.00   53
  9  \w    -81.00 -37.00   1.00   30.00    --   -7.86 151.00  94.83   44
 10  \w    -70.00 -29.00   1.00   30.00    --   -7.86 135.00 154.18   41
 11  \w    -81.00 -37.00   1.00   30.00    --   -7.86 151.00-142.38   44
 12  \w    -83.00 -38.00   1.00   30.00    --   -7.86 153.00 -79.97   45
 13  \w    -65.00 -24.00   1.00   30.00    --   -7.86 126.00  -4.28   41
 14  \w    -16.00  83.00   1.00   30.00    --    8.41  38.00 -30.00   99
 15  \w    -66.00  33.00   1.00   30.00    --    8.41 -38.00 -60.00   99
 16  \w    -66.00  33.00   1.00   30.00    --    8.41 -38.00  60.00   99
 17  \w    -80.00  42.00   1.00   30.00    --    8.41   0.00-180.00  122
 18  \w    -16.00  83.00   1.00   30.00    --    8.41  38.00 150.00   99
;
_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      0.0089701000
_diffrn_orient_matrix_UB_12      -0.0444757000
_diffrn_orient_matrix_UB_13      0.0507648000
_diffrn_orient_matrix_UB_21      -0.0707099000
_diffrn_orient_matrix_UB_22      -0.0191603000
_diffrn_orient_matrix_UB_23      -0.0021102000
_diffrn_orient_matrix_UB_31      0.0382698000
_diffrn_orient_matrix_UB_32      -0.0445816000
_diffrn_orient_matrix_UB_33      -0.0230519000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            48191
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.828
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.023
_diffrn_reflns_theta_min         2.781
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.838
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66388
_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    1.362
_exptl_crystal_description       prism
_exptl_crystal_F_000             548
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.382
_refine_diff_density_min         -0.387
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 4268 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     573
_refine_ls_number_reflns         11387
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0428
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0420P)^2^+0.2023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0786
_refine_ls_wR_factor_ref         0.0846
_reflns_Friedel_coverage         0.876
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.773
_reflns_number_gt                10067
_reflns_number_total             11387
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk315221st
_cod_original_cell_volume        1290.81(5)
_cod_database_code               7713126
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c27 h35 Cl1 n2 Pd1'
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.752
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.66
_olex2_refinement_description
;
1. 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
2. Uiso/Uaniso restraints and constraints
C22 \\sim C24: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01
C22 \\sim C23: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01
C49 \\sim C50: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
3.a Riding coordinates:
 C26(H26), C53(H53)
3.b Ternary CH refined with riding coordinates:
 C22(H22), C49(H49)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C17(H17), C18(H18), C19(H19), C20(H20),
 C34(H34), C35(H35), C36(H36), C37(H37), C44(H44), C45(H45), C46(H46), C47(H47)
3.d X=CH2 refined with riding coordinates:
 C25(H25A,H25B), C27(H27A,H27B), C52(H52A,H52B), C54(H54A,H54B)
3.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C)
;
_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 2.427
_oxdiff_exptl_absorpt_empirical_full_min 0.469