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_7713128
_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         'C46 H41 Cl N2 Pd, C0.5 Cl1, 0.5(C3 H6)'
_chemical_formula_sum            'C48 H44.5 Cl2 N2 Pd'
_chemical_formula_weight         826.65
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-01-29
_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                102.2810(10)
_cell_angle_beta                 101.4300(10)
_cell_angle_gamma                91.4670(10)
_cell_formula_units_Z            2
_cell_length_a                   11.0273(2)
_cell_length_b                   11.7303(2)
_cell_length_c                   17.0058(2)
_cell_measurement_reflns_used    48773
_cell_measurement_temperature    295
_cell_measurement_theta_max      27.5810
_cell_measurement_theta_min      3.3670
_cell_volume                     2101.51(6)
_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      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.902
_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    -65.00 -24.00   1.00   10.00    --   -8.02 126.00-159.85   41
  2  \w    -67.00 -27.00   1.00   10.00    --   -8.02 129.00 -46.44   40
  3  \w    -24.00  84.00   1.00   10.00    --    8.25  77.00 -30.00  108
  4  \w    -16.00  83.00   1.00   10.00    --    8.25  38.00 120.00   99
  5  \w    -66.00  33.00   1.00   10.00    --    8.25 -38.00 -60.00   99
  6  \w    -16.00  83.00   1.00   10.00    --    8.25  38.00-120.00   99
  7  \w    -66.00  33.00   1.00   10.00    --    8.25 -38.00  60.00   99
  8  \w    -20.00  49.00   1.00   10.00    --    8.25 -99.00-180.00   69
  9  \w    -62.00 -20.00   1.00   10.00    --   -8.02 121.00   7.61   42
 10  \w    -67.00 -27.00   1.00   10.00    --   -8.02 129.00 126.18   40
 11  \w    -75.00 -33.00   1.00   10.00    --   -8.02 142.00  48.63   42
 12  \w    -77.00 -34.00   1.00   10.00    --   -8.02 145.00 -99.87   43
 13  \w    -63.00 -22.00   1.00   10.00    --   -8.02 123.00-121.09   41
 14  \w    -80.00  96.00   1.00   10.00    --    8.25   0.00-180.00  176
 15  \w    -66.00  33.00   1.00   10.00    --    8.25 -38.00-150.00   99
 16  \w    -80.00  96.00   1.00   10.00    --    8.25   0.00-120.00  176
 17  \w    -80.00  96.00   1.00   10.00    --    8.25   0.00 -90.00  176
 18  \w    -80.00  96.00   1.00   10.00    --    8.25   0.00-150.00  176
;
_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      -0.0086965000
_diffrn_orient_matrix_UB_12      0.0589202000
_diffrn_orient_matrix_UB_13      0.0175769000
_diffrn_orient_matrix_UB_21      0.0651997000
_diffrn_orient_matrix_UB_22      0.0119998000
_diffrn_orient_matrix_UB_23      0.0122425000
_diffrn_orient_matrix_UB_31      0.0012305000
_diffrn_orient_matrix_UB_32      0.0152716000
_diffrn_orient_matrix_UB_33      -0.0380270000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.902
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            94003
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.902
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.583
_diffrn_reflns_theta_min         2.799
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.603
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90494
_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    1.306
_exptl_crystal_description       prism
_exptl_crystal_F_000             853
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.769
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         9686
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0656P)^2^+1.0817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1116
_refine_ls_wR_factor_ref         0.1193
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8531
_reflns_number_total             9686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01182h2.cif
_cod_data_source_block           lk41062meso
_cod_original_formula_sum        'C48 H44.50 Cl2 N2 Pd'
_cod_database_code               7713128
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c46 h42 Cl1 n2 Pd1'
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.869
_reflns_odcompleteness_completeness 99.80
_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. Restrained distances
 C50-C49
 1.54 with sigma of 0.005
 C49-C48
 1.54 with sigma of 0.005
 C53-C52
 1.54 with sigma of 0.005
 C52-C51
 1.54 with sigma of 0.005
 C50-C48_$1
 1.54 with sigma of 0.005
 C48-C50_$1
 1.54 with sigma of 0.005
 C47-Cl2
 1.7 with sigma of 0.005
 C47-Cl3
 1.7 with sigma of 0.005
 C47-Cl4
 1.7 with sigma of 0.005
 C47-Cl5
 1.7 with sigma of 0.005
 C47-Cl6
 1.7 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C47 \\sim Cl2: within 1.8A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C50) = Uanis(C53)
Uanis(C52) = Uanis(C49)
Uanis(C48) = Uanis(C51)
4. Rigid body (RIGU) restrains
 C48, C49, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C51, C52, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl2, Cl3, Cl4, Cl5, Cl6, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: Cl2(0.2) Cl3(0.2) Cl4(0.2) Cl5(0.2) Cl6(0.2) C47(0.5) C48(0.25)
 H48A(0.25) H48B(0.25) C49(0.25) H49A(0.25) H49B(0.25) C50(0.25) H50A(0.25)
 H50B(0.25) C51(0.25) H51B(0.25) H51A(0.25) C52(0.25) H52A(0.25) H52B(0.25)
 C53(0.25) H53B(0.25) H53A(0.25)
6.a Riding coordinates:
 C45(H45)
6.b Ternary CH refined with riding coordinates:
 C12(H12), C31(H31)
6.c Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51B,H51A), C52(H52A,
 H52B), C53(H53B,H53A)
6.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27),
  C28(H28), C29(H29), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
 C39(H39), C40(H40), C41(H41), C42(H42), C43(H43)
6.e X=CH2 refined with riding coordinates:
 C44(H44A,H44B), C46(H46A,H46B)
6.f 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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.304
_oxdiff_exptl_absorpt_empirical_full_min 0.749