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_1573475
_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_absolute_configuration unk
_chemical_formula_moiety         'C14 H18 Cl2 N4 O Pd'
_chemical_formula_sum            'C14 H18 Cl2 N4 O Pd'
_chemical_formula_weight         435.62
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-11T15:12:08-00:00
_audit_update_record
;
2024-12-04 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            4
_cell_length_a                   8.91557(12)
_cell_length_b                   10.26115(13)
_cell_length_c                   18.9836(2)
_cell_measurement_reflns_used    54838
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      33.115
_cell_measurement_theta_min      2.238
_cell_volume                     1736.70(4)
_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    -28.00  21.00   0.50    0.30    --   13.07  99.00 148.00   98
  2  \w    -18.00  54.00   0.50    0.30    --   13.07 -99.00  42.00  144
  3  \w    -55.00  21.00   0.50    0.30    --  -13.54  99.00 148.00  152
  4  \w    -19.00  29.00   0.50    0.30    --  -13.54 -99.00  42.00   96
  5  \w     -8.00  90.00   0.50    0.30    --   13.07  57.00  60.00  196
  6  \w     -8.00  90.00   0.50    0.30    --   13.07  57.00-150.00  196
  7  \w     -8.00  90.00   0.50    0.30    --   13.07  57.00 -30.00  196
  8  \w    -25.00  67.00   0.50    0.30    --  -13.54  19.00 -90.00  184
  9  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00   8.90  118
 10  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00-153.00  118
 11  \w    -25.00  67.00   0.50    0.30    --  -13.54  19.00  90.00  184
 12  \w    -25.00  67.00   0.50    0.30    --  -13.54  19.00   0.00  184
 13  \w    -68.00  28.00   0.50    0.30    --   13.07 -19.00 150.00  192
 14  \w    -25.00  67.00   0.50    0.30    --  -13.54  19.00 -60.00  184
 15  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00 113.36  118
 16  \w    -74.00 -17.00   0.50    0.30    --  -13.54 130.00 -27.00  114
 17  \w    -87.00 -42.00   0.50    0.30    --  -13.54-178.00  60.00   90
 18  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00  70.78  118
 19  \w    -78.00 -20.00   0.50    0.30    --  -13.54 136.00 169.69  116
 20  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00 -86.99  118
 21  \w    -19.00  29.00   0.50    0.30    --  -13.54 -99.00  60.00   96
 22  \w    -79.00 -21.00   0.50    0.30    --  -13.54 138.00  97.18  116
 23  \w     -8.00  19.00   0.50    0.30    --   13.07  57.00-180.00   54
 24  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00-129.87  118
 25  \w    -80.00 -21.00   0.50    0.30    --  -13.54 139.00  35.05  118
;
_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      -0.0260363
_diffrn_orient_matrix_UB_12      -0.0650673
_diffrn_orient_matrix_UB_13      -0.0029165
_diffrn_orient_matrix_UB_21      -0.0266346
_diffrn_orient_matrix_UB_22      0.0026213
_diffrn_orient_matrix_UB_23      0.0351803
_diffrn_orient_matrix_UB_31      -0.0703291
_diffrn_orient_matrix_UB_32      0.023157
_diffrn_orient_matrix_UB_33      -0.012222
_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  0.0409
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            105258
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.504
_diffrn_reflns_theta_min         2.146
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.382
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.561
_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            orange
_exptl_crystal_density_diffrn    1.666
_exptl_crystal_description       needle
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.338
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.069
_refine_diff_density_max         1.154
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.49(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         5302
_refine_ls_number_restraints     226
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.033
_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^)+(0.0300P)^2^+1.5001P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0763
_refine_ls_wR_factor_ref         0.0781
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    1
_reflns_Friedel_fraction_max     1
_reflns_number_gt                4819
_reflns_number_total             5302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01337a2.cif
_cod_data_source_block           23MA063_MA-055
_cod_depositor_comments
'Adding full bibliography for 1573473--1573476.cif.'
_cod_database_code               1573475
_shelx_estimated_absorpt_t_min   0.652
_shelx_estimated_absorpt_t_max   0.911
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.246
_oxdiff_exptl_absorpt_empirical_full_min 0.884
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Twinned data refinement
 Scales: 0.51(7)
 0.49(7)
        2. 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
        3. Shared sites
        {C2, N1A}
        {C2A, N1}
        4. Restrained distances
 N1-C7 \\sim N1A-C7A
 with sigma of 0.002
 C2A-C6A \\sim C6-C2
 with sigma of 0.002
 C13-C12 \\sim C14A-C12 \\sim C14-C12 \\sim C13A-C12
 with sigma of 0.002
 O1A-C8A \\sim O1-C8
 with sigma of 0.002
        5. Rigid bond restraints
 C7, N1, C1, C2, C6, C5, C3, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C8, C9, C10, C11, O1, N4, C12, C13, C14, N3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6A, C2A, C1, N1A, C7A, C3, C4, C5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N1, C5, C1, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1A, N2A, C8A, C9A, C10A, N4A, C12, C11A, C14A, C13A, N3A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl1, Cl1A, Pd1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        6. Uiso/Uaniso restraints and constraints
        Uanis(C6A) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C6)
        \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
        Uanis(Cl1) \\sim Ueq, Uanis(Cl1A) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.01
        Uanis(O1A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10A)
        \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C10) \\sim Ueq,
        Uanis(O1) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.01
        Uanis(C8A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
        Uanis(N4A) \\sim Ueq, Uanis(N3A) \\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(N2)
        \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(N4) \\sim Ueq: with sigma of 0.01 and
        sigma for terminal atoms of 0.02
        Uanis(C2) = Uanis(N1A)
        Uanis(C2A) = Uanis(N1)
        7. Others
 Sof(H12A)=Sof(O1A)=Sof(C8A)=Sof(C9A)=Sof(C11A)=Sof(H11A)=Sof(C13A)=Sof(H13D)=
 Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C10A)=
 Sof(H10A)=Sof(N4A)=Sof(N3A)=Sof(N2A)=1-FVAR(1)
 Sof(N2)=Sof(N3)=Sof(H12)=Sof(N4)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(C8)=Sof(O1)=FVAR(1)
 Sof(Cl1A)=1-FVAR(2)
 Sof(Cl1)=FVAR(2)
 Sof(H5B)=Sof(H3B)=Sof(N1A)=Sof(C2A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-FVAR(3)
 Sof(C2)=Sof(N1)=Sof(H5A)=Sof(H3A)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(3)
        8.a Ternary CH refined with riding coordinates:
 C12(H12), C12(H12A)
        8.b Aromatic/amide H refined with riding coordinates:
 C5(H5A), C5(H5B), C4(H4), C3(H3A), C3(H3B), C11A(H11A), C10A(H10A), C10(H10),
 C11(H11)
        8.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C), C14A(H14D,
 H14E,H14F), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,
 H7AB,H7AC)
;
_shelx_res_checksum              11061
_shelx_hkl_checksum              24852