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_1573474
_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         'C19 H20 Cl2 N4 O Pd'
_chemical_formula_sum            'C19 H20 Cl2 N4 O Pd'
_chemical_formula_weight         497.69
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-16T17:04:23-00:00
_audit_update_record
;
2024-10-30 deposited with the CCDC.	2024-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.0469(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.62997(6)
_cell_length_b                   14.78476(7)
_cell_length_c                   11.92053(6)
_cell_measurement_reflns_used    34688
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      79.765
_cell_measurement_theta_min      2.999
_cell_volume                     1979.415(18)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_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
_diffrn_measured_fraction_theta_full 1
_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    -77.00 -19.00   0.50    0.24    --  -23.00 137.00 -96.00  116
  2  \w    -74.00 -16.00   0.50    0.24    --  -23.00 132.00  86.00  116
  3  \w    -70.00 -12.00   0.50    0.24    --  -23.00 125.00 -90.00  116
  4  \w    -21.00   5.00   0.50    0.24    --  -23.00 -88.00 -25.19   52
  5  \w    -70.00 -12.00   0.50    0.24    --  -23.00 125.00 120.00  116
  6  \w    -95.00  -6.00   0.50    0.24    --  -23.00 -61.00   0.00  178
  7  \w    -95.00   0.00   0.50    0.24    --  -23.00 -77.00 150.00  190
  8  \w    -25.00  40.00   0.50    0.24    --   47.92 -38.00 -90.00  130
  9  \w    -25.00  40.00   0.50    0.24    --   47.92 -38.00   0.00  130
 10  \w    -26.00  23.00   0.50    0.24    --   47.92 -19.00-150.00   98
 11  \w    -25.00  40.00   0.50    0.24    --   47.92 -38.00-180.00  130
 12  \w    -26.00  23.00   0.50    0.24    --   47.92 -19.00  30.00   98
 13  \w    -23.00  63.00   0.50    0.24    --   47.92 -57.00 -30.00  172
 14  \w     42.00  68.00   0.50    0.80    --  113.25 -61.00  60.00   52
 15  \w     42.00  68.00   0.50    0.80    --  113.25 -61.00 120.00   52
 16  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00 -90.00  128
 17  \w     97.00 177.00   0.50    0.80    --  113.25  61.00   0.00  160
 18  \w    101.00 177.00   0.50    0.80    --  113.25  30.00 150.00  152
 19  \w     42.00 102.00   0.50    0.80    --  113.25 -77.00  30.00  120
 20  \w    100.00 177.00   0.50    0.80    --  113.25  15.00 -90.00  154
 21  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00   0.00  128
 22  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00-180.00  128
 23  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00  30.00  128
 24  \w    101.00 177.00   0.50    0.80    --  113.25  45.00-150.00  152
 25  \w    101.00 177.00   0.50    0.80    --  113.25  30.00 -30.00  152
 26  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00 -30.00  128
 27  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00-150.00  128
 28  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00 -60.00  128
 29  \w    100.00 177.00   0.50    0.80    --  113.25  15.00  90.00  154
 30  \w     42.00 102.00   0.50    0.80    --  113.25 -77.00 120.00  120
 31  \w     42.00  68.00   0.50    0.80    --  113.25 -61.00-120.00   52
 32  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00 120.00  128
 33  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00-120.00  128
 34  \w    101.00 177.00   0.50    0.80    --  113.25  45.00-180.00  152
 35  \w    101.00 177.00   0.50    0.80    --  113.25  45.00  30.00  152
 36  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00  90.00  128
 37  \w     42.00  68.00   0.50    0.80    --  113.25 -61.00  30.00   52
 38  \w     42.00 102.00   0.50    0.80    --  113.25 -77.00 150.00  120
 39  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00  60.00  128
 40  \w     42.00  68.00   0.50    0.80    --  113.25 -61.00-150.00   52
 41  \w     42.00 102.00   0.50    0.80    --  113.25 -77.00-180.00  120
 42  \w     97.00 177.00   0.50    0.80    --  113.25  61.00 -30.00  160
 43  \w    101.00 177.00   0.50    0.80    --  113.25  45.00 -90.00  152
 44  \w     42.00 109.00   0.50    0.80    --  113.25-114.00  35.04  134
 45  \w     25.00 121.00   0.50    0.24    --   47.92  77.00   0.00  192
 46  \w     25.00 121.00   0.50    0.24    --   47.92  77.00-180.00  192
 47  \w     25.00 121.00   0.50    0.24    --   47.92  77.00  90.00  192
 48  \w     25.00 121.00   0.50    0.24    --   47.92  77.00 -60.00  192
 49  \w     25.00 121.00   0.50    0.24    --   47.92  77.00 -90.00  192
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0683971
_diffrn_orient_matrix_UB_12      -0.0638919
_diffrn_orient_matrix_UB_13      -0.0618171
_diffrn_orient_matrix_UB_21      -0.055381
_diffrn_orient_matrix_UB_22      -0.0822884
_diffrn_orient_matrix_UB_23      0.0455843
_diffrn_orient_matrix_UB_31      -0.105212
_diffrn_orient_matrix_UB_32      0.0018057
_diffrn_orient_matrix_UB_33      -0.1096329
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0381
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            39723
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.73
_diffrn_reflns_theta_min         4.733
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.184
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.51465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.67
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.434
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.06
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.17
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         4006
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0238
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0234P)^2^+2.2183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0615
_refine_ls_wR_factor_ref         0.0615
_reflns_Friedel_coverage         0
_reflns_number_gt                3994
_reflns_number_total             4006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01337a2.cif
_cod_data_source_block           22MA060_ER-0474
_cod_depositor_comments
'Adding full bibliography for 1573473--1573476.cif.'
_cod_database_code               1573474
_shelx_estimated_absorpt_t_min   0.318
_shelx_estimated_absorpt_t_max   0.536
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.319
_oxdiff_exptl_absorpt_empirical_full_min 0.703
_shelx_shelxl_version_number     2018/3
_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, All C(H,H,H,H,H,H) groups
        2. Rigid bond restraints
 C5A, C1, C2, C3, N1A, C4, C6, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        3. Uiso/Uaniso restraints and constraints
Uanis(N1A) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
Uanis(C5A) \\sim Ueq, Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
        4. Others
 Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=Sof(H7BD)=Sof(H7BE)=Sof(H7BF)=Sof(H4B)=Sof(H2B)=
 Sof(C5A)=Sof(N1A)=1-FVAR(1)
 Sof(N1)=Sof(C5)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(H4A)=Sof(H2A)=FVAR(1)
        5.a Me refined with riding coordinates:
 C1(H1BD,H1BE,H1BF), C7(H7BD,H7BE,H7BF)
        5.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C10(H10), C17(H17), C13(H13), C4(H4A), C4(H4B), C2(H2A), C2(H2B),
 C15(H15), C3(H3)
        5.c Idealised Me refined as rotating group:
 C1(H1AA,H1AB,H1AC), C7(H7AA,H7AB,H7AC), C19(H19A,H19B,H19C), C18(H18A,H18B,
 H18C)
;
_shelx_res_checksum              63489
_shelx_hkl_checksum              7668