Tunable bis(pyridinium amidate) ligands efficiently promote palladium-catalyzed ethylene polymerization
Reusser, Esaïe; Albrecht, Martin; Catalysis Science & Technology  (2025) –; doi:10.1039/D5CY01102G

data_1576133
_publ_section_title
;
 Tunable bis(pyridinium amidate) ligands efficiently promote
 palladium-catalyzed ethylene polymerization
;
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_paper_doi               10.1039/D5CY01102G
_journal_year                    2025
_chemical_formula_moiety         'C38 H48 F12 K N10 O4 P2 Pd2, 0.5(F6 P)'
_chemical_formula_sum            'C38 H48 F15 K N10 O4 P2.5 Pd2'
_chemical_formula_weight         1323.19
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-21T10:29:49-00:00
_audit_update_record
;
2025-04-02 deposited with the CCDC.	2025-10-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.7682(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4383(2)
_cell_length_b                   22.0849(3)
_cell_length_c                   13.37677(12)
_cell_measurement_reflns_used    48053
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      78.903
_cell_measurement_theta_min      2.9
_cell_volume                     6176.79(12)
_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  (Sheldrick, 2015)'
_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    -55.00  28.00   0.50    0.50    --  -23.00  97.00-141.00  166
  2  \w     -6.00  80.00   0.50    0.50    --   47.92 -97.00 110.00  172
  3  \w    107.00 177.00   0.50    6.00    --  113.25  97.00-141.00  140
  4  \w     42.00 106.00   0.50    6.00    --  113.25 -97.00 110.00  128
  5  \w    -97.00 -10.00   0.50    0.50    --  -23.00 -19.00 150.00  174
  6  \w    -96.00 -10.00   0.50    0.50    --  -23.00 -38.00  90.00  172
  7  \w    -28.00  52.00   0.50    0.50    --  -23.00  15.00  30.00  160
  8  \w    -94.00  -8.00   0.50    0.50    --  -23.00 -57.00  30.00  172
  9  \w    -36.00  49.00   0.50    0.50    --  -23.00  45.00-150.00  170
 10  \w    -70.00 -12.00   0.50    0.50    --  -23.00 125.00 150.00  116
 11  \w     33.00 120.00   0.50    0.50    --   47.92  57.00 -60.00  174
 12  \w    -25.00  40.00   0.50    0.50    --   47.92 -38.00-180.00  130
 13  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00 -60.00   52
 14  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00 120.00   52
 15  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00  30.00   52
 16  \w     42.00 107.00   0.50    6.00    --  113.25-103.00   7.68  130
 17  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00  30.00  128
 18  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00-150.00   52
 19  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00 -30.00   52
 20  \w     91.00 177.00   0.50    6.00    --  113.25  77.00-120.00  172
 21  \w     97.00 177.00   0.50    6.00    --  113.25  61.00  90.00  160
 22  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00-180.00  128
 23  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00 150.00  120
 24  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00-180.00   52
 25  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00  60.00  120
 26  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00 120.00  120
 27  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00-120.00  128
 28  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00 -30.00  120
 29  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00 150.00  128
 30  \w    101.00 177.00   0.50    6.00    --  113.25  30.00-150.00  152
 31  \w     97.00 177.00   0.50    6.00    --  113.25  61.00-180.00  160
 32  \w     97.00 177.00   0.50    6.00    --  113.25  61.00 -60.00  160
 33  \w     91.00 177.00   0.50    6.00    --  113.25  77.00 150.00  172
 34  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00-180.00  120
 35  \w     95.00 177.00   0.50    6.00    --  113.25  65.00 -85.12  164
 36  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00-150.00  128
 37  \w    101.00 177.00   0.50    6.00    --  113.25  79.00-141.69  152
 38  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00 120.00  128
 39  \w     91.00 177.00   0.50    6.00    --  113.25  77.00 -60.00  172
 40  \w     93.00 177.00   0.50    6.00    --  113.25  70.00 -26.19  168
 41  \w     97.00 177.00   0.50    6.00    --  113.25  61.00 -90.00  160
 42  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00  60.00  128
 43  \w     97.00 177.00   0.50    6.00    --  113.25  61.00 -30.00  160
 44  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00   0.00   52
 45  \w     42.00 102.00   0.50    6.00    --  113.25 -77.00  30.00  120
 46  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00-120.00   52
 47  \w     42.00 106.00   0.50    6.00    --  113.25 -94.00 -90.00  128
 48  \w     48.00  77.00   0.50    6.00    --  113.25 -94.00-125.76   58
 49  \w     79.00 106.00   0.50    6.00    --  113.25 -94.00-125.76   54
 50  \w    150.00 175.00   0.50    6.00    --  113.25  61.00   0.00   50
 51  \w    150.00 176.00   0.50    6.00    --  113.25  15.00 -30.00   52
 52  \w     42.00  68.00   0.50    6.00    --  113.25 -61.00 -90.00   52
;
_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      -0.0071576
_diffrn_orient_matrix_UB_12      0.063301
_diffrn_orient_matrix_UB_13      -0.0495194
_diffrn_orient_matrix_UB_21      -0.0667886
_diffrn_orient_matrix_UB_22      -0.0174389
_diffrn_orient_matrix_UB_23      -0.0627575
_diffrn_orient_matrix_UB_31      -0.0301397
_diffrn_orient_matrix_UB_32      0.0235863
_diffrn_orient_matrix_UB_33      0.0870198
_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  0.0499
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            125948
_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         75.574
_diffrn_reflns_theta_min         2.91
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.694
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.468
_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            yellow
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       needle
_exptl_crystal_F_000             2646
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.992
_refine_diff_density_min         -0.943
_refine_diff_density_rms         0.093
_refine_ls_extinction_coef       0.00041(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     864
_refine_ls_number_reflns         12833
_refine_ls_number_restraints     480
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0604
_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^)+(0.1294P)^2^+2.2741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1887
_refine_ls_wR_factor_ref         0.1972
_reflns_Friedel_coverage         0
_reflns_number_gt                10885
_reflns_number_total             12833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy01102g2.cif
_cod_data_source_block           22MA010_ER-0292
_cod_original_cell_volume        6176.78(11)
_cod_original_formula_sum        'C38 H48 F15 K N10 O4 P2.50 Pd2'
_cod_database_code               1576133
_shelx_estimated_absorpt_t_min   0.311
_shelx_estimated_absorpt_t_max   0.575
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.151
_oxdiff_exptl_absorpt_empirical_full_min 0.654
_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. Restrained distances
 P3-F16 = P3-F17 = P3-F18 = P3-F15 = P3-F14 = P3-F13
 1.65 with sigma of 0.02
 P4-F24 = P4-F19 = P4-F22 = P4-F20 = P4-F21 = P4-F23
 1.65 with sigma of 0.02
 C37A-N10A
 1.137 with sigma of 0.01
 C37A-C38A
 1.456 with sigma of 0.01
 C37-N10
 1.137 with sigma of 0.01
 C38A-N10A
 2.593 with sigma of 0.02
 C37-C38
 1.456 with sigma of 0.01
 C38-N10
 2.593 with sigma of 0.02
 F21-F19 \\sim F19-F23 \\sim F23-F20 \\sim F20-F21
 with sigma of 0.002
 F24-F21 \\sim F24-F19 \\sim F24-F23 \\sim F24-F20
 with sigma of 0.002
 F22-F21 \\sim F22-F19 \\sim F22-F23 \\sim F22-F20
 with sigma of 0.002
 F16-F18 \\sim F17-F15 \\sim F13-F14
 with sigma of 0.05
 P3-F16 \\sim P3-F17 \\sim P3-F18 \\sim P3-F15 \\sim P3-F14 \\sim P3-F13
 with sigma of 0.02
 F16-F17 \\sim F16-F15 \\sim F16-F14 \\sim F16-F13 \\sim F18-F17 \\sim F18-F15
        \\sim F18-F14 \\sim F18-F13
 with sigma of 0.04
        3. Rigid bond restraints
 F6, P1, F3, F2, F5, F1, F4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C36, C36A, Pd2A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C36, Pd2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        4. Uiso/Uaniso restraints and constraints
P3 \\sim F16 \\sim F17 \\sim F18 \\sim F15 \\sim F14 \\sim F13: within 2A with
        sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F20)
\\sim Ueq, Uanis(P4) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F21) \\sim Ueq:
        with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38A) \\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(N10A) \\sim Ueq: with sigma
        of 0.02 and sigma for terminal atoms of 0.01
Uanis(C37) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(F12) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F9A) \\sim Ueq, Uanis(F12A)
\\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F8) \\sim Ueq,
Uanis(F11A) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F10)
\\sim Ueq, Uanis(F9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
        of 0.02
Uanis(N10) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.2
Uanis(F5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(N6) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(N7)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C24) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.01
Uanis(P3) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18)
\\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F13) \\sim Ueq:
        with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        5. Rigid body (RIGU) restrains
 P3, F16, F17, F18, F15, F14, F13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
        6. Others
 Sof(N10A)=Sof(C37A)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(Pd2A)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(Pd2)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(N10)=Sof(C37)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
 Sof(F9A)=Sof(F12A)=Sof(F7A)=Sof(F11A)=Sof(F10A)=Sof(F8A)=1-FVAR(2)
 Sof(F10)=Sof(F8)=Sof(F7)=Sof(F9)=Sof(F11)=Sof(F12)=FVAR(2)
 Fixed Sof: P3(0.25) F16(0.25) F17(0.25) F18(0.25) F15(0.25) F14(0.25)
 F13(0.25) P4(0.25) F24(0.25) F19(0.25) F22(0.25) F20(0.25) F21(0.25) F23(0.25)
        7.a Aromatic/amide H refined with riding coordinates:
 C33(H33), C7(H7), C14(H14), C6(H6), C13(H13), C32(H32), C31(H31), C12(H12),
 C5(H5), C24(H24), C25(H25), C26(H26)
        7.b Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C17(H17A,H17B,
 H17C), C16(H16A,H16B,H16C), C9(H9A,H9B,H9C), C28(H28A,H28B,H28C), C36(H36A,
 H36B,H36C), C35(H35A,H35B,H35C), C19(H19A,H19B,H19C), C27(H27A,H27B,H27C),
 C38(H38A,H38B,H38C), C38A(H38D,H38E,H38F), C36A(H36D,H36E,H36F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              67633
_shelx_fab_checksum              28998