Combining hydrogen bonding interactions with steric and electronic modifications for thermally robust α-diimine palladium catalysts toward ethylene (co)polymerization
Zheng, Handou; Zhong, Liu; Du, Cheng; Du, Wenbo; Cheung, Chi Shing; Ruan, Jingjing; Gao, Haiyang; Catalysis Science & Technology 11 (2021) 124–135; doi:10.1039/D0CY01617A

data_1559573
_publ_section_title
;
 Combining hydrogen bonding interactions with steric and electronic
 modifications for thermally robust \a-diimine palladium catalysts toward
 ethylene (co)polymerization
;
_journal_issue                   1
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              124
_journal_page_last               135
_journal_paper_doi               10.1039/D0CY01617A
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety
'C43 H48 I2 N3 Pd, C32 H12 B F24, 0.5(C6 H14)'
_chemical_formula_sum            'C78 H67 B F24 I2 N3 Pd'
_chemical_formula_weight         1873.35
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2020-08-04 deposited with the CCDC.	2020-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                98.154(2)
_cell_angle_beta                 96.070(2)
_cell_angle_gamma                99.498(2)
_cell_formula_units_Z            2
_cell_length_a                   13.0060(4)
_cell_length_b                   16.8630(5)
_cell_length_c                   19.2164(6)
_cell_measurement_reflns_used    11767
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.8920
_cell_measurement_theta_min      3.8000
_cell_volume                     4078.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.946
_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    -66.00  29.00   1.00    1.90    --  -41.14  38.00 120.00   95
  2  \w    -74.00  24.00   1.00    1.90    --  -41.14  77.00-150.00   98
  3  \w   -115.00 -17.00   1.00    1.90    --  -41.14 -38.00 -60.00   98
  4  \w     49.00 118.00   1.00    7.65    --  107.79-125.00-120.00   69
  5  \w     39.00 131.00   1.00    7.65    --  107.79 -30.00 -60.00   92
  6  \w     82.00 178.00   1.00    7.65    --  107.79  45.00 -30.00   96
  7  \w    102.00 160.00   1.00    7.65    --  107.79 125.00-120.00   58
  8  \w     32.00 139.00   1.00    7.65    --  107.79 -77.00-120.00  107
  9  \w     39.00 118.00   1.00    7.65    --  107.79-125.00 120.00   79
 10  \w    103.00 165.00   1.00    7.65    --  107.79 125.00 -90.00   62
 11  \w     32.00 135.00   1.00    7.65    --  107.79 -15.00 150.00  103
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0561516000
_diffrn_orient_matrix_UB_12      0.0738191000
_diffrn_orient_matrix_UB_13      0.0043169000
_diffrn_orient_matrix_UB_21      0.0187509000
_diffrn_orient_matrix_UB_22      0.0090358000
_diffrn_orient_matrix_UB_23      -0.0765424000
_diffrn_orient_matrix_UB_31      -0.1057138000
_diffrn_orient_matrix_UB_32      -0.0572828000
_diffrn_orient_matrix_UB_33      -0.0282575000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0677
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            24442
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.319
_diffrn_reflns_theta_min         3.847
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.639
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44311
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_description       plate
_exptl_crystal_F_000             1858
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.488
_refine_diff_density_min         -1.068
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1028
_refine_ls_number_reflns         15742
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0635
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1097P)^2^+4.8869P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1706
_refine_ls_wR_factor_ref         0.1843
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13387
_reflns_number_total             15742
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy01617a2.cif
_cod_data_source_block           18121202
_cod_depositor_comments
'Adding full bibliography for 1559569--1559575.cif.'
_cod_database_code               1559573
_chemical_oxdiff_formula         'C H O N I Pd Cl B F'
_chemical_oxdiff_usercomment     C3b
_reflns_odcompleteness_completeness 98.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2. Restrained distances
 F25-F23
 2.2 with sigma of 0.02
 C62-F25
 1.4 with sigma of 0.02
3. Rigid bond restraints
 F22, F25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(F25) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F20) \\sim Ueq, Uanis(F26) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F22) = Uanis(F25)
Uanis(F20) = Uanis(F26)
5. Others
 Sof(F20)=1-FVAR(1)
 Sof(F26)=FVAR(1)
 Fixed Sof: C76(0.5) H76A(0.5) H76B(0.5) H76C(0.5) C77(0.5) H77A(0.5)
 H77B(0.5) C78(0.5) H78A(0.5) H78B(0.5) C79(0.5) H79A(0.5) H79B(0.5) C80(0.5)
 H80A(0.5) H80B(0.5) C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) F22(0.8) F25(0.2)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C20(H20), C46(H46), C51(H51), C63(H63), C69(H69)
6.b Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C11(H11), C13(H13), C14(H14), C18(H18), C21(H21), C25(H25),
 C28(H28), C31(H31), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40),
  C41(H41), C43(H43), C44(H44), C47(H47), C48(H48), C49(H49), C53(H53), C54(H54)
6.d Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C71(H71A,H71B,H71C), C72(H72A,
 H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C81(H81A,H81B,H81C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.118
_oxdiff_exptl_absorpt_empirical_full_min 0.650