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_7713124
_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         'C50 H49 Cl N2 Pd, C6 H13.5'
_chemical_formula_sum            'C56 H62.5 Cl N2 Pd'
_chemical_formula_weight         905.43
_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             2019-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-20 deposited with the CCDC.	2023-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.002(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9780(2)
_cell_length_b                   33.5142(7)
_cell_length_c                   15.1164(3)
_cell_measurement_reflns_used    30503
_cell_measurement_temperature    293
_cell_measurement_theta_max      24.8480
_cell_measurement_theta_min      3.3410
_cell_volume                     5051.91(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 0.906
_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  33.00   1.00   30.00    --   -7.86 -99.00   0.00   53
  2  \w    -32.00  66.00   1.00   30.00    --   -7.86  38.00-120.00   98
  3  \w    -16.00  83.00   1.00   30.00    --    8.41  38.00-150.00   99
  4  \w    -64.00  37.00   1.00   30.00    --    8.41 -57.00  60.00  101
  5  \w    -64.00  37.00   1.00   30.00    --    8.41 -57.00 -90.00  101
  6  \w    -32.00  66.00   1.00   30.00    --   -7.86  38.00 150.00   98
  7  \w    -20.00  33.00   1.00   30.00    --   -7.86 -99.00 -60.00   53
  8  \w    -20.00  33.00   1.00   30.00    --   -7.86 -99.00-150.00   53
  9  \w    -20.00  27.00   1.00   30.00    --    8.41 -99.00  30.00   47
;
_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      0.0469881000
_diffrn_orient_matrix_UB_12      0.0079096000
_diffrn_orient_matrix_UB_13      0.0315931000
_diffrn_orient_matrix_UB_21      0.0356494000
_diffrn_orient_matrix_UB_22      0.0090304000
_diffrn_orient_matrix_UB_23      -0.0345277000
_diffrn_orient_matrix_UB_31      -0.0397580000
_diffrn_orient_matrix_UB_32      0.0174385000
_diffrn_orient_matrix_UB_33      0.0035436000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0867
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.906
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            93978
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.635
_diffrn_reflns_theta_min         2.780
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.456
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62940
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.190
_exptl_crystal_description       needle
_exptl_crystal_F_000             1902
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.889
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         11759
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.1041
_refine_ls_R_factor_gt           0.0632
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0721P)^2^+6.4445P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1596
_refine_ls_wR_factor_ref         0.1800
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7854
_reflns_number_total             11759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk4061meso
_cod_original_formula_sum        'C56 H62.50 Cl N2 Pd'
_cod_database_code               7713124
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c50 h50 Cl2 n2 Pd1'
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.804
_reflns_odcompleteness_completeness 99.77
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C59-C60
 1.45 with sigma of 0.02
 C60-C61
 1.45 with sigma of 0.02
 C61-C62
 1.45 with sigma of 0.02
 C62-C56
 1.45 with sigma of 0.02
 C56-C57
 1.45 with sigma of 0.02
 C52-C53
 1.45 with sigma of 0.02
 C53-C54
 1.45 with sigma of 0.02
 C54-C55
 1.45 with sigma of 0.02
 C55-C56
 1.45 with sigma of 0.02
 C57-C58
 1.54 with sigma of 0.02
 C51-C52
 1.54 with sigma of 0.02
 C51-C59
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim
C59 \\sim C60 \\sim C61 \\sim C62: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01
Pd1 \\sim C48 \\sim C49 \\sim C50: within 2.3A with sigma of 0.005 and sigma
for terminal atoms of 0.01
4. Others
 Fixed Sof: C51(0.75) H51A(0.5) H51B(0.5) H51C(0.5) H51D(0.25) H51E(0.25)
 H51F(0.25) C52(0.5) H52A(0.5) H52B(0.5) C53(0.5) H53A(0.5) H53B(0.5) C54(0.5)
 H54A(0.5) H54B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C56(0.75) H56B(0.5) H56A(0.5)
 H56D(0.25) H56C(0.25) C57(0.75) H57A(0.75) H57B(0.75) C58(0.75) H58A(0.75)
 H58B(0.75) H58C(0.75) C59(0.25) H59A(0.25) H59B(0.25) C60(0.25) H60A(0.25)
 H60B(0.25) C61(0.25) H61A(0.25) H61B(0.25) C62(0.25) H62A(0.25) H62B(0.25)
5.a Riding coordinates:
 C48(H48B,H48A), C49(H49), C50(H50B,H50A)
5.b Ternary CH refined with riding coordinates:
 C14(H14), C35(H35)
5.c Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56B,
 H56A), C56(H56D,H56C), C57(H57A,H57B), C59(H59A,H59B), C60(H60A,H60B),
 C61(H61A,H61B), C62(H62A,H62B)
5.d 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), C37(H37), C38(H38),
  C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47)
5.e Idealised Me refined with riding coordinates:
 C51(H51A,H51B,H51C), C51(H51D,H51E,H51F), C58(H58A,H58B,H58C)
5.f 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)
;
_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 2.578
_oxdiff_exptl_absorpt_empirical_full_min 0.348