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_7713125
_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         'C44 H45 Cl N2 Pd'
_chemical_formula_sum            'C44 H45 Cl N2 Pd'
_chemical_formula_weight         743.67
_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   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc26sbr3
_audit_creation_date             2020-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-08 deposited with the CCDC.	2023-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6877(3)
_cell_length_b                   16.4427(3)
_cell_length_c                   16.8054(4)
_cell_measurement_reflns_used    21489
_cell_measurement_temperature    295
_cell_measurement_theta_max      25.3840
_cell_measurement_theta_min      3.8360
_cell_volume                     3782.27(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.918
_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    -98.00  77.00   1.00   15.00    --   -9.59   3.00-143.00  175
  2  \w    -20.00  31.00   1.00   15.00    --   -9.59 -99.00  90.00   51
  3  \w    -34.00  65.00   1.00   15.00    --   -9.59  38.00  60.00   99
  4  \w    -20.00  31.00   1.00   15.00    --   -9.59 -99.00  30.00   51
  5  \w    -14.00  84.00   1.00   15.00    --   10.05  38.00 -90.00   98
  6  \w      6.00  41.00   1.00   15.00    --   10.05-132.00-147.00   35
  7  \w    -66.00  43.00   1.00   15.00    --   10.05 -77.00 -60.00  109
;
_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      0.0205352000
_diffrn_orient_matrix_UB_12      0.0018995000
_diffrn_orient_matrix_UB_13      0.0387066000
_diffrn_orient_matrix_UB_21      0.0475752000
_diffrn_orient_matrix_UB_22      -0.0008019000
_diffrn_orient_matrix_UB_23      -0.0167223000
_diffrn_orient_matrix_UB_31      -0.0000745000
_diffrn_orient_matrix_UB_32      0.0430840000
_diffrn_orient_matrix_UB_33      -0.0020278000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0883
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.918
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            55929
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.994
_diffrn_reflns_theta_min         3.224
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83783
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.81a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       prism
_exptl_crystal_F_000             1544
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.575
_refine_diff_density_min         -0.861
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         9003
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0489P)^2^+1.5191P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1192
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                7145
_reflns_number_total             9003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk31202nd
_cod_database_code               7713125
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'c44 h45 Cl1 n2 Pd1'
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.851
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.04(4)
 -0.04(4)
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 Riding coordinates:
 C36(H36A,H36B), C37(H37), C38(H38)
3.b Ternary CH refined with riding coordinates:
 C14(H14)
3.c Aromatic/amide H refined with riding coordinates:
 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), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44)
3.d 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), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              8392
_shelx_hkl_checksum              12441
_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 3.628
_oxdiff_exptl_absorpt_empirical_full_min 0.760