Enhancing activity and selectivity of palladium catalysts in ketone α-arylation by tailoring the imine chelate of pyridinium amidate (PYA) ligands.
Reusser, Esaïe; Aeschlimann, Michael; Albrecht, Martin; Catalysis science & technology 15 (2025) 867–877; doi:10.1039/d4cy01337a

data_1573476
_publ_section_title
;
 Enhancing activity and selectivity of palladium catalysts in ketone
 &#x3b1;-arylation by tailoring the imine chelate of pyridinium amidate
 (PYA) ligands.
;
_journal_issue                   3
_journal_name_full               'Catalysis science &amp; technology'
_journal_page_first              867
_journal_page_last               877
_journal_paper_doi               10.1039/d4cy01337a
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C12 H14 Cl2 N4 O Pd'
_chemical_formula_sum            'C12 H14 Cl2 N4 O Pd'
_chemical_formula_weight         407.57
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      56
_symmetry_space_group_name_Hall  '-P 2ab 2ac'
_symmetry_space_group_name_H-M   'P c c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-16T15:51:08-00:00
_audit_update_record
;
2024-10-30 deposited with the CCDC.	2024-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.97050(13)
_cell_length_b                   23.0363(2)
_cell_length_c                   14.07250(15)
_cell_measurement_reflns_used    71695
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      33.546
_cell_measurement_theta_min      2.503
_cell_volume                     3556.40(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1
_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    -18.00  55.00   0.50    0.60    --   13.29 -99.00 112.00  146
  2  \w    -28.00  21.00   0.50    0.60    --   13.29  99.00-141.00   98
  3  \w    -55.00  21.00   0.50    0.60    --  -13.44  99.00-141.00  152
  4  \w    -19.00  29.00   0.50    0.60    --  -13.44 -99.00 112.00   96
  5  \w    -25.00  94.00   0.50    0.60    --   13.29  19.00  90.00  238
  6  \w    -87.00 -42.00   0.50    0.60    --  -13.44-178.00  60.00   90
  7  \w    -94.00   7.00   0.50    0.60    --  -13.44 -38.00-120.00  202
  8  \w    -19.00  29.00   0.50    0.60    --  -13.44 -99.00-120.00   96
  9  \w    -90.00   8.00   0.50    0.60    --  -13.44 -57.00   0.00  196
 10  \w     -8.00  90.00   0.50    0.60    --   13.29  57.00-180.00  196
 11  \w    -18.00  37.00   0.50    0.60    --   13.29 -99.00  30.00  110
 12  \w    -87.00 -42.00   0.50    0.60    --  -13.44-178.00-120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0217934
_diffrn_orient_matrix_UB_12      -0.0282309
_diffrn_orient_matrix_UB_13      0.0107587
_diffrn_orient_matrix_UB_21      -0.0575342
_diffrn_orient_matrix_UB_22      0.0072757
_diffrn_orient_matrix_UB_23      -0.0196613
_diffrn_orient_matrix_UB_31      0.0198503
_diffrn_orient_matrix_UB_32      -0.0099151
_diffrn_orient_matrix_UB_33      -0.0451484
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            102018
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.506
_diffrn_reflns_theta_min         2.056
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.344
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.704
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
        Numerical absorption correction based on gaussian integration over
        a multifaceted crystal model
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       block
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.314
_exptl_crystal_size_mid          0.224
_exptl_crystal_size_min          0.184
_refine_diff_density_max         0.52
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.11
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         5437
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.11
_refine_ls_R_factor_all          0.0247
_refine_ls_R_factor_gt           0.0227
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0265P)^2^+2.4681P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0603
_refine_ls_wR_factor_ref         0.0611
_reflns_Friedel_coverage         0
_reflns_number_gt                5064
_reflns_number_total             5437
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01337a2.cif
_cod_data_source_block           23MA069_MA-013
_cod_depositor_comments
'Adding full bibliography for 1573473--1573476.cif.'
_cod_original_cell_volume        3556.40(7)
_cod_database_code               1573476
_shelx_estimated_absorpt_t_min   0.678
_shelx_estimated_absorpt_t_max   0.79
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.25
_oxdiff_exptl_absorpt_empirical_full_min 0.815
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C10(H10), C3(H3), C9(H9)
        2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              18301
_shelx_hkl_checksum              19518
_shelx_fab_checksum              8297