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_1559574
_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
'C45 H54 N3 O2 Pd, C32 H12 B F24, 0.25(C H2 Cl2)'
_chemical_formula_sum            'C77.25 H66.5 B Cl0.5 F24 N3 O2 Pd'
_chemical_formula_weight         1659.77
_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     direct
_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                109.704(4)
_cell_angle_beta                 107.844(4)
_cell_angle_gamma                95.369(3)
_cell_formula_units_Z            2
_cell_length_a                   14.4315(6)
_cell_length_b                   16.2211(6)
_cell_length_c                   18.6665(8)
_cell_measurement_reflns_used    6893
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.5040
_cell_measurement_theta_min      3.8630
_cell_volume                     3820.3(3)
_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    'SIR2004 (Burla et al., 2007)'
_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 0.989
_diffrn_measured_fraction_theta_max 0.948
_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   -114.00 -13.00   1.00    6.00    --  -41.14 -57.00-180.00  101
  2  \w   -116.00  -9.00   1.00    6.00    --  -41.14 -77.00 -60.00  107
  3  \w    -92.00  -2.00   1.00    6.00    --  -41.14 125.00  30.00   90
  4  \w     47.00 158.00   1.00   12.00    --  108.42 -15.00 120.00  111
  5  \w     35.00  94.00   1.00   12.00    --  108.42-125.00  30.00   59
  6  \w     52.00 117.00   1.00   12.00    --  108.42-125.00  90.00   65
  7  \w     92.00 174.00   1.00   12.00    --  108.42  30.00 -30.00   82
  8  \w     48.00 117.00   1.00   12.00    --  108.42-125.00-150.00   69
  9  \w     55.00 115.00   1.00   12.00    --  108.42-125.00 -30.00   60
 10  \w     32.00 113.00   1.00   12.00    --  108.42 -30.00 -60.00   81
 11  \w     38.00 122.00   1.00   12.00    --  108.42 -45.00  30.00   84
 12  \w     47.00 138.00   1.00   12.00    --  108.42 -61.00 150.00   91
 13  \w    -92.00  -9.00   1.00    6.00    --  -41.14 -77.00  30.00   83
 14  \w    -90.00 -73.00   1.00    6.00    --  -41.14 -77.00 120.00   17
;
_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      -0.0111778000
_diffrn_orient_matrix_UB_12      -0.1023885000
_diffrn_orient_matrix_UB_13      -0.0271925000
_diffrn_orient_matrix_UB_21      0.0781857000
_diffrn_orient_matrix_UB_22      0.0038727000
_diffrn_orient_matrix_UB_23      -0.0400972000
_diffrn_orient_matrix_UB_31      0.0835265000
_diffrn_orient_matrix_UB_32      0.0139400000
_diffrn_orient_matrix_UB_33      0.0805375000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.0889
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25386
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.612
_diffrn_reflns_theta_min         3.922
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.059
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85174
_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            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1685
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.013
_refine_diff_density_min         -1.216
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1083
_refine_ls_number_reflns         14830
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0973
_refine_ls_R_factor_gt           0.0767
_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^)+(0.0946P)^2^+5.9151P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2011
_refine_ls_wR_factor_ref         0.2201
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11527
_reflns_number_total             14830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy01617a2.cif
_cod_data_source_block           19032703
_cod_depositor_comments
'Adding full bibliography for 1559569--1559575.cif.'
_cod_original_formula_sum        'C77.25 H66.50 B Cl0.50 F24 N3 O2 Pd'
_cod_database_code               1559574
_chemical_oxdiff_formula         'C H O N Pb B F'
_chemical_oxdiff_usercomment     Pd_OMe
_reflns_odcompleteness_completeness 99.01
_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. Rigid bond restraints
 F26, F17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C67, C60, C32, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F23, F28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C67 \\sim C64 \\sim C60 \\sim C65: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
F23 \\sim F28: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Cl1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C67) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(F26) = Uanis(F17)
4. Others
 Sof(F13)=1-FVAR(1)
 Sof(F25)=FVAR(1)
 Sof(F18)=1-FVAR(2)
 Sof(F27)=FVAR(2)
 Sof(F23)=1-FVAR(3)
 Sof(F28)=FVAR(3)
 Fixed Sof: O1(0.65) H37(0.35) H40(0.65) O2(0.65) H60(0.65) F17(0.75)
 H64(0.35) O2A(0.35) O1A(0.35) Cl2(0.25) C74(0.65) H74A(0.65) H74B(0.65)
 H74C(0.65) C77(0.65) H77A(0.65) H77B(0.65) H77C(0.65) C78(0.35) H78A(0.35)
 H78B(0.35) H78C(0.35) C79(0.35) H79A(0.35) H79B(0.35) H79C(0.35) Cl1(0.25)
 C80(0.25) H80A(0.25) H80B(0.25) F26(0.25)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C20(H20), C21(H21), C62(H62), C71(H71)
5.b Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C9(H9), C18(H18), C19(H19), C25(H25), C26(H26), C27(H27),
 C29(H29), C30(H30), C33(H33), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40),
  C41(H41), C42(H42), C46(H46), C52(H52), C54(H54), C57(H57), C60(H60),
 C64(H64), C65(H65), C67(H67)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C44(H44A,H44B,H44C), C51(H51A,H51B,H51C), C55(H55A,H55B,
 H55C), C58(H58A,H58B,H58C), C61(H61A,H61B,H61C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C)
;
_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 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.737