Enhanced suppression of chain transfer in ethylene (co)polymerization via synergistic axial substituent effects in pyridine-imine Ni(ii) and Pd(ii) catalysts
Fan, Huijun; Ma, Mengya; Dai, Shengyu; Polymer Chemistry 16 (2025) 4764–4773; doi:10.1039/D5PY00857C

data_1576029
_publ_section_title
;
 Enhanced suppression of chain transfer in ethylene (co)polymerization via
 synergistic axial substituent effects in pyridine-imine Ni(ii) and Pd(ii)
 catalysts
;
_journal_issue                   43
_journal_name_full               'Polymer Chemistry'
_journal_page_first              4764
_journal_page_last               4773
_journal_paper_doi               10.1039/D5PY00857C
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C51 H43 Cl N2 Pd'
_chemical_formula_sum            'C51 H43 Cl N2 Pd'
_chemical_formula_weight         825.72
_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   geom
_audit_creation_date             2025-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-05-06 deposited with the CCDC.	2025-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                92.890(2)
_cell_angle_beta                 95.260(3)
_cell_angle_gamma                106.440(4)
_cell_formula_units_Z            2
_cell_length_a                   7.9650(8)
_cell_length_b                   11.2240(12)
_cell_length_c                   27.180(3)
_cell_measurement_reflns_used    2770
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      28.593
_cell_measurement_theta_min      2.453
_cell_volume                     2313.3(4)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.3002
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            7920
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        25.019
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_min         1.898
_exptl_absorpt_coefficient_mu    0.492
_exptl_absorpt_correction_T_max  0.9854
_exptl_absorpt_correction_T_min  0.9479
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             852
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.279
_refine_diff_density_min         -1.002
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         7920
_refine_ls_number_restraints     234
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.3027
_refine_ls_R_factor_gt           0.1684
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3794
_refine_ls_wR_factor_ref         0.4372
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2757
_reflns_number_total             7920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5py00857c2.cif
_cod_data_source_block           220808a
_cod_depositor_comments
'Adding full bibliography for 1576028--1576029.cif.'
_cod_database_code               1576029
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.948
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.77(12)
 0.23(12)
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. Restrained distances
 C45-C46 = C46-C47 = C47-C48 = C48-C49 = C49-C50 = C50-C45
 1.39 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50: within 3.8A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 3.8A
Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C6) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(N2) \\sim Ueq,
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C51') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C42) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(Cl1) = Uanis(C51') = Uanis(Cl1') = Uanis(C51)
5. Others
 Sof(Cl1')=Sof(C51')=Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(1)
 Sof(Cl1)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C31(H31)
6.b Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B)
6.c Me refined with riding coordinates:
 C51(H51A,H51B,H51C), C51'(H51D,H51E,H51F)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C10(H10), C15(H15), C16(H16), C17(H17),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C33(H33), C37(H37), C36(H36), C35(H35), C34(H34),
 C41(H41), C40(H40), C39(H39), C43(H43), C42(H42), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50)
6.e Fitted hexagon refined as free rotating group:
 C20(C21,C22,C23,C24,C19), C33(C32,C37,C36,C35,C34), C41(C40,C39,C38,C43,C42)
6.f Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              12046
_shelx_hkl_checksum              63660
_olex2_submission_special_instructions 'No special instructions were received'