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_7713122
_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         'C32 H33 Cl N2 Pd, C0.5 H2 Cl'
_chemical_formula_sum            'C32.5 H35 Cl2 N2 Pd'
_chemical_formula_weight         630.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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                 96.7570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.35660(10)
_cell_length_b                   17.0040(2)
_cell_length_c                   18.8780(2)
_cell_measurement_reflns_used    36465
_cell_measurement_temperature    293
_cell_measurement_theta_max      70.9780
_cell_measurement_theta_min      4.7280
_cell_volume                     2982.62(6)
_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 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -42.00  57.00   1.00    2.00    --  -17.77  38.00 120.00   99
  2  \w    -94.00  15.00   1.00    2.00    --  -17.77 -77.00 120.00  109
  3  \w   -107.00 -35.00   1.00    2.00    --  -17.77-178.00-150.00   72
  4  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00-180.00   99
  5  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00  30.00   99
  6  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00   0.00   99
  7  \w     57.00 107.00   1.00    2.00    --   17.77 178.00-150.00   50
  8  \w     17.00  69.00   1.00    2.00    --   17.77-117.00  88.00   52
  9  \w    -15.00  94.00   1.00    2.00    --   17.77  77.00  30.00  109
 10  \w     69.00 178.00   1.00   25.00    --  101.41  77.00   0.00  109
 11  \w     94.00 175.00   1.00   25.00    --  101.41 125.00 -90.00   81
 12  \w     72.00 174.00   1.00   25.00    --  101.41  61.00  30.00  102
 13  \w     69.00 178.00   1.00   25.00    --  101.41  77.00 -30.00  109
 14  \w     76.00 174.00   1.00   25.00    --  101.41  45.00  60.00   98
 15  \w     69.00 178.00   1.00   25.00    --  101.41  77.00  30.00  109
 16  \w     25.00 130.00   1.00   25.00    --  101.41 -30.00 -90.00  105
 17  \w     72.00 174.00   1.00   25.00    --  101.41  61.00   0.00  102
 18  \w     94.00 175.00   1.00   25.00    --  101.41 125.00-180.00   81
 19  \w     19.00 109.00   1.00   25.00    --  101.41 -94.00-150.00   90
 20  \w     76.00 174.00   1.00   25.00    --  101.41  45.00  90.00   98
 21  \w     25.00 134.00   1.00   25.00    --  101.41 -77.00 -90.00  109
 22  \w     49.00 178.00   1.00   25.00    --  101.41  15.00  90.00  129
 23  \w     73.00 178.00   1.00   25.00    --  101.41  30.00  90.00  105
 24  \w     20.00 154.00   1.00   25.00    --  101.41 -15.00 150.00  134
 25  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00 -90.00   99
 26  \w    -94.00  15.00   1.00    2.00    --  -17.77 -77.00-180.00  109
 27  \w    -91.00  10.00   1.00    2.00    --  -17.77 -57.00-120.00  101
 28  \w    -42.00  57.00   1.00    2.00    --  -17.77  38.00  30.00   99
 29  \w    -98.00  23.00   1.00    2.00    --  -17.77 -19.00-120.00  121
 30  \w    -69.00   5.00   1.00    2.00    --  -17.77 117.00 175.00   74
 31  \w     57.00 107.00   1.00    2.00    --   17.77 178.00 -60.00   50
 32  \w     69.00 178.00   1.00   25.00    --  101.41  77.00-180.00  109
 33  \w     28.00 121.00   1.00   25.00    --  101.41-125.00 150.00   93
 34  \w     72.00 174.00   1.00   25.00    --  101.41  61.00 120.00  102
 35  \w     72.00 174.00   1.00   25.00    --  101.41  61.00 -60.00  102
 36  \w     72.00 174.00   1.00   25.00    --  101.41  61.00-120.00  102
 37  \w     69.00 178.00   1.00   25.00    --  101.41  77.00-150.00  109
 38  \w     72.00 174.00   1.00   25.00    --  101.41  61.00 150.00  102
 39  \w     72.00 174.00   1.00   25.00    --  101.41  61.00  90.00  102
 40  \w     76.00 174.00   1.00   25.00    --  101.41  45.00-180.00   98
 41  \w     72.00 174.00   1.00   25.00    --  101.41  61.00 -30.00  102
 42  \w     72.00 174.00   1.00   25.00    --  101.41  61.00-180.00  102
 43  \w     72.00 174.00   1.00   25.00    --  101.41  61.00 -90.00  102
 44  \w     72.00 174.00   1.00   25.00    --  101.41  61.00-150.00  102
 45  \w     76.00 174.00   1.00   25.00    --  101.41  45.00 -90.00   98
 46  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00  90.00   99
 47  \w    -91.00  10.00   1.00    2.00    --  -17.77 -57.00  90.00  101
 48  \w    -94.00  15.00   1.00    2.00    --  -17.77 -77.00  90.00  109
 49  \w    -92.00   7.00   1.00    2.00    --  -17.77 -38.00-120.00   99
 50  \w      1.00  59.00   1.00    2.00    --   17.77 -99.00 -30.00   58
 51  \w      1.00  59.00   1.00    2.00    --   17.77 -99.00-180.00   58
 52  \w     55.00 105.00   1.00    2.00    --   17.77-178.00  30.00   50
 53  \w     69.00 106.00   1.00   25.00    --  101.41  77.00 120.00   37
 54  \w     69.00 178.00   1.00   25.00    --  101.41  77.00 -60.00  109
 55  \w     69.00 178.00   1.00   25.00    --  101.41  77.00  90.00  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      -0.0951255000
_diffrn_orient_matrix_UB_12      -0.0192907000
_diffrn_orient_matrix_UB_13      0.0589882000
_diffrn_orient_matrix_UB_21      -0.1171343000
_diffrn_orient_matrix_UB_22      -0.0325928000
_diffrn_orient_matrix_UB_23      -0.0565574000
_diffrn_orient_matrix_UB_31      0.0687406000
_diffrn_orient_matrix_UB_32      -0.0823058000
_diffrn_orient_matrix_UB_33      0.0085550000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            76642
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.318
_diffrn_reflns_theta_min         3.509
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.836
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47791
_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    1.405
_exptl_crystal_description       needle
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.701
_refine_diff_density_min         -1.104
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         5777
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0877P)^2^+2.1579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1331
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5341
_reflns_number_total             5777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk2087a
_cod_original_formula_sum        'C32.50 H35 Cl2 N2 Pd'
_cod_database_code               7713122
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c32 h29 Cl1 n2 Pd1'
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.342
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C34
 1.75 with sigma of 0.005
3. Rigid bond restraints
 Cl2, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Cl2 \\sim C34: within 1.8A with sigma of 0.001 and sigma for terminal atoms of
0.001
Uanis(C31) = Uanis(C32)
5. Rigid body (RIGU) restrains
 C24, C29, C25, C28, C26, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: C31(0.75) H31(0.75) C32(0.25) H32(0.25) C34(0.5)
7.a Riding coordinates:
 C30(H30A,H30B), C30(H30C,H30D), C31(H31), C33(H33A,H33B), C33(H33C,H33D),
 C32(H32), C34(H34A,H34B)
7.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C17(H17), C16(H16), C15(H15), C14(H14),
 C13(H13), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29)
7.c Fitted hexagon refined as free rotating group:
 C24(C25,C26,C27,C28,C29)
7.d 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 2.727
_oxdiff_exptl_absorpt_empirical_full_min 0.526