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_7713129
_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         'C21 H31 Cl N2 Pd'
_chemical_formula_sum            'C21 H31 Cl N2 Pd'
_chemical_formula_weight         453.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc26sbs4
_audit_creation_date             2018-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_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            8
_cell_length_a                   17.2249(3)
_cell_length_b                   14.0349(3)
_cell_length_c                   18.3854(4)
_cell_measurement_reflns_used    17066
_cell_measurement_temperature    293
_cell_measurement_theta_max      27.6340
_cell_measurement_theta_min      3.9820
_cell_volume                     4444.67(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.18b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.18b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.18b (Rigaku OD, 2015)'
_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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.903
_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    -16.00  83.00   1.00   13.50    --    8.41  38.00-150.00   99
  2  \w    -20.00  49.00   1.00   13.50    --    8.41 -99.00  90.00   69
  3  \w    -16.00  83.00   1.00   13.50    --    8.41  38.00 -60.00   99
  4  \w    -16.00  35.00   1.00   13.50    --    8.41  38.00  30.00   51
  5  \w    -68.00  41.00   1.00   13.50    --    8.41 -77.00-120.00  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      -0.0315764000
_diffrn_orient_matrix_UB_12      0.0156243000
_diffrn_orient_matrix_UB_13      -0.0216876000
_diffrn_orient_matrix_UB_21      0.0263940000
_diffrn_orient_matrix_UB_22      0.0165962000
_diffrn_orient_matrix_UB_23      -0.0267794000
_diffrn_orient_matrix_UB_31      -0.0012375000
_diffrn_orient_matrix_UB_32      -0.0451003000
_diffrn_orient_matrix_UB_33      -0.0173654000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.903
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            47668
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.621
_diffrn_reflns_theta_min         3.241
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.961
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.18b (Rigaku Oxford Diffraction, 2015)
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    1.355
_exptl_crystal_description       prism
_exptl_crystal_F_000             1872
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         5147
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0223P)^2^+4.2023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0654
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3959
_reflns_number_total             5147
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk2069
_cod_database_code               7713129
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.802
_reflns_odcompleteness_completeness 99.58
_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
C19 \\sim C20: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01
C20 \\sim C21: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01
3.a Riding coordinates:
 C19(H19A,H19B), C20(H20), C21(H21A,H21B)
3.b Ternary CH refined with riding coordinates:
 C4(H4), C16(H16)
3.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B)
3.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14)
3.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_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 1.176
_oxdiff_exptl_absorpt_empirical_full_min 0.865