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_7713123
_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         'C26 H33 Cl N2 Pd'
_chemical_formula_sum            'C26 H33 Cl N2 Pd'
_chemical_formula_weight         515.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-01-23
_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                 96.214(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6459(2)
_cell_length_b                   21.2509(3)
_cell_length_c                   12.3138(2)
_cell_measurement_reflns_used    31514
_cell_measurement_temperature    293
_cell_measurement_theta_max      27.8180
_cell_measurement_theta_min      3.9120
_cell_volume                     2509.30(8)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.946
_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   10.00    --    8.41  38.00-180.00   99
  2  \w    -20.00  49.00   1.00   10.00    --    8.41 -99.00-120.00   69
  3  \w    -20.00  82.00   1.00   10.00    --    8.41  57.00-150.00  102
  4  \w    -16.00  83.00   1.00   10.00    --    8.41  38.00   0.00   99
  5  \w    -24.00  85.00   1.00   10.00    --    8.41  77.00  30.00  109
  6  \w    -41.00  24.00   1.00   10.00    --   -7.78  81.00  70.00   65
  7  \w    -20.00  49.00   1.00   10.00    --    8.41 -99.00 -30.00   69
  8  \w    -64.00  37.00   1.00   10.00    --    8.41 -57.00-180.00  101
  9  \w    -20.00  49.00   1.00   10.00    --    8.41 -99.00-180.00   69
 10  \w    -20.00  49.00   1.00   10.00    --    8.41 -99.00 -90.00   69
 11  \w    -64.00  37.00   1.00   10.00    --    8.41 -57.00 120.00  101
 12  \w    -64.00  37.00   1.00   10.00    --    8.41 -57.00  60.00  101
 13  \w    -20.00  49.00   1.00   10.00    --    8.41 -99.00  30.00   69
 14  \w    -64.00 -39.00   1.00   10.00    --    8.41 -57.00 -90.00   25
;
_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      0.0327488000
_diffrn_orient_matrix_UB_12      0.0284022000
_diffrn_orient_matrix_UB_13      -0.0134827000
_diffrn_orient_matrix_UB_21      0.0242266000
_diffrn_orient_matrix_UB_22      0.0046654000
_diffrn_orient_matrix_UB_23      0.0558818000
_diffrn_orient_matrix_UB_31      0.0617558000
_diffrn_orient_matrix_UB_32      -0.0168918000
_diffrn_orient_matrix_UB_33      -0.0072485000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            75805
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.608
_diffrn_reflns_theta_min         3.193
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.860
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77801
_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    1.364
_exptl_crystal_description       prism
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.557
_refine_diff_density_min         -0.450
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         6070
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0290
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0329P)^2^+1.3851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0688
_refine_ls_wR_factor_ref         0.0735
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5140
_reflns_number_total             6070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk2078
_cod_database_code               7713123
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.875
_reflns_odcompleteness_completeness 99.71
_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.a Riding coordinates:
 C24(H24A,H24B), C25(H25), C26(H26A,H26B)
2.b Ternary CH refined with riding coordinates:
 C12(H12), C21(H21)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_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 1.340
_oxdiff_exptl_absorpt_empirical_full_min 0.745