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_7713127
_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 unk
_chemical_formula_moiety         'C32 H29 Cl N2 Pd'
_chemical_formula_sum            'C32 H29 Cl N2 Pd'
_chemical_formula_weight         583.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2023-03-20 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                   18.4645(5)
_cell_length_b                   10.3454(3)
_cell_length_c                   14.2625(4)
_cell_measurement_reflns_used    9262
_cell_measurement_temperature    293
_cell_measurement_theta_max      26.2030
_cell_measurement_theta_min      3.6140
_cell_volume                     2724.46(13)
_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 0.994
_diffrn_measured_fraction_theta_max 0.916
_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    -20.00  82.00   1.00   15.00    --    8.41  57.00-120.00  102
  2  \w    -24.00  85.00   1.00   15.00    --    8.41  77.00 -30.00  109
  3  \w    -20.00  49.00   1.00   15.00    --    8.41 -99.00  60.00   69
  4  \w    -64.00 -39.00   1.00   15.00    --    8.41 -57.00 -90.00   25
  5  \w    -20.00  49.00   1.00   15.00    --    8.41 -99.00-150.00   69
;
_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      0.0112909000
_diffrn_orient_matrix_UB_12      -0.0368694000
_diffrn_orient_matrix_UB_13      0.0392954000
_diffrn_orient_matrix_UB_21      0.0088336000
_diffrn_orient_matrix_UB_22      -0.0522672000
_diffrn_orient_matrix_UB_23      -0.0300825000
_diffrn_orient_matrix_UB_31      0.0356309000
_diffrn_orient_matrix_UB_32      0.0246970000
_diffrn_orient_matrix_UB_33      -0.0049924000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25700
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.604
_diffrn_reflns_theta_min         3.284
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.802
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72944
_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    1.422
_exptl_crystal_description       plate
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.940
_refine_diff_density_min         -1.004
_refine_diff_density_rms         0.124
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.19(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         6064
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0592
_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^)+(0.1231P)^2^+1.4530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1676
_refine_ls_wR_factor_ref         0.1795
_reflns_Friedel_coverage         0.928
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                5176
_reflns_number_total             6064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk2087b
_cod_database_code               7713127
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.819
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.66
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.81(7)
 0.19(7)
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:
 C30(H30A,H30B), C31(H31), C32(H32A,H32B)
3.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29)
3.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C)
;
_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 1.650
_oxdiff_exptl_absorpt_empirical_full_min 0.788