Unexpected o-aryl tBu group effect on suppression of chain transfer in pyridine–imine Ni(ii) and Pd(ii) catalyzed ethylene (co)polymerization
Yan, Zhengpeng; Zou, Wenping; Dai, Shengyu; Polymer Chemistry 14 (2023) 2107–2116; doi:10.1039/D3PY00146F

data_1568725
_publ_section_title
;
 Unexpected o-aryl tBu group effect on suppression of chain transfer in
 pyridine--imine Ni(ii) and Pd(ii) catalyzed ethylene (co)polymerization
;
_journal_issue                   17
_journal_name_full               'Polymer Chemistry'
_journal_page_first              2107
_journal_page_last               2116
_journal_paper_doi               10.1039/D3PY00146F
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C86 H80 Br4 N4 Ni2'
_chemical_formula_sum            'C86 H80 Br4 N4 Ni2'
_chemical_formula_weight         1606.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-11-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-11-20 deposited with the CCDC.	2023-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.285(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.718(2)
_cell_length_b                   9.0100(11)
_cell_length_c                   21.438(2)
_cell_measurement_reflns_used    4155
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      26.366
_cell_measurement_theta_min      2.408
_cell_volume                     3998.6(7)
_computing_cell_refinement       'SAINT v6.02A (Bruker, 2001)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v6.02A (Bruker, 2001)'
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     0.3171
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            7025
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.020
_diffrn_reflns_theta_max         25.020
_diffrn_reflns_theta_min         1.901
_exptl_absorpt_coefficient_mu    2.514
_exptl_absorpt_correction_T_max  0.9284
_exptl_absorpt_correction_T_min  0.5722
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1640
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.843
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.851
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     420
_refine_ls_number_reflns         7025
_refine_ls_number_restraints     497
_refine_ls_restrained_S_all      0.834
_refine_ls_R_factor_all          0.2689
_refine_ls_R_factor_gt           0.1063
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1045P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2299
_refine_ls_wR_factor_ref         0.2830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2200
_reflns_number_total             7025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3py00146f2.cif
_cod_data_source_block           221115a
_cod_depositor_comments
'Adding full bibliography for 1568725--1568726.cif.'
_cod_original_cell_volume        3998.6(8)
_cod_database_code               1568725
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.572
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.81(8)
 0.19(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C11-C31' = C31'-C32' = C31'-C38'
 1.5 with sigma of 0.01
 C38'-C40' = C40'-C42' = C42'-C38' = C39'-C41' = C41'-C43' = C43'-C39'
 2.37 with sigma of 0.02
 C32'-C34' = C34'-C36' = C36'-C32' = C33'-C35' = C35'-C37' = C37'-C33'
 2.37 with sigma of 0.02
 C38'-C39' = C39'-C40' = C40'-C41' = C41'-C42' = C42'-C43' = C43'-C38'
 1.39 with sigma of 0.01
 C32'-C33' = C33'-C34' = C34'-C35' = C35'-C36' = C36'-C37' = C37'-C32'
 1.39 with sigma of 0.01
 C11-C31 = C31-C32 = C31-C38
 1.5 with sigma of 0.01
 C38-C40 = C40-C42 = C42-C38 = C39-C41 = C41-C43 = C43-C39
 2.37 with sigma of 0.02
 C32-C34 = C34-C36 = C36-C32 = C33-C35 = C35-C37 = C37-C33
 2.37 with sigma of 0.02
 C38-C39 = C39-C40 = C40-C41 = C41-C42 = C42-C43 = C43-C38
 1.39 with sigma of 0.01
 C32-C33 = C33-C34 = C34-C35 = C35-C36 = C36-C37 = C37-C32
 1.39 with sigma of 0.01
 C31'-C39' \\sim C31'-C43' \\sim C31'-C33' \\sim C31'-C37'
 with sigma of 0.02
4. Restrained planarity
 C31', C32', C33', C34', C35', C36', C37'
 with sigma of 0.02
5. Rigid bond restraints
 C28, C27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C31 \\sim C32 \\sim
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim
C41 \\sim C42 \\sim C43: within 3.8A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 3.8A
Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 3.8
Uanis(C43) = Uanis(C43')
Uanis(C42) = Uanis(C42')
Uanis(C41) = Uanis(C41')
Uanis(C40) = Uanis(C40')
Uanis(C39) = Uanis(C39')
Uanis(C38) = Uanis(C38')
Uanis(C37) = Uanis(C37')
Uanis(C36) = Uanis(C36')
Uanis(C35) = Uanis(C35')
Uanis(C34) = Uanis(C34')
Uanis(C33) = Uanis(C33')
Uanis(C32) = Uanis(C32')
Uanis(C31) = Uanis(C31')
7. Others
 Sof(C31')=Sof(H31')=Sof(C32')=Sof(C33')=Sof(H33')=Sof(C34')=Sof(H34')=
 Sof(C35')=Sof(H35')=Sof(C36')=Sof(H36')=Sof(C37')=Sof(H37')=Sof(C38')=
 Sof(C39')=Sof(H39')=Sof(C40')=Sof(H40')=Sof(C41')=Sof(H41')=Sof(C42')=
 Sof(H42')=Sof(C43')=Sof(H43')=1-FVAR(1)
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=
 Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=Sof(H39)=
 Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=FVAR(1)
8.a :
 C32(C33,C34,C35,C36,C37,C38,C39,C40,C41,C42,C43), C32'(C33',C34',C35',C36',
 C37',C38',C39',C40',C41',C42',C43')
8.b Ternary CH refined with riding coordinates:
 C18(H18), C31(H31), C31'(H31')
8.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C10(H10), C12(H12), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
  C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40),
 C41(H41), C42(H42), C43(H43), C33'(H33'), C34'(H34'), C35'(H35'), C36'(H36'),
 C37'(H37'), C39'(H39'), C40'(H40'), C41'(H41'), C42'(H42'), C43'(H43')
8.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              5489
_olex2_submission_special_instructions 'No special instructions were received'