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_1559569
_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 Cl2 N3 Pd, C32 H12 B F24'
_chemical_formula_sum            'C75 H60 B Cl2 F24 N3 Pd'
_chemical_formula_weight         1647.37
_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   mixed
_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                69.1710(10)
_cell_angle_beta                 75.0500(10)
_cell_angle_gamma                81.7150(10)
_cell_formula_units_Z            2
_cell_length_a                   12.48880(10)
_cell_length_b                   16.9952(2)
_cell_length_c                   19.3546(2)
_cell_measurement_reflns_used    43179
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.5130
_cell_measurement_theta_min      3.9340
_cell_volume                     3703.33(7)
_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 0.999
_diffrn_measured_fraction_theta_max 0.977
_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     14.00  39.00   1.00    3.00    --   46.00  83.00   2.18   25
  2  \w     36.00  62.00   1.00    3.00    --   66.00  77.00 -12.29   26
  3  \w     58.00  96.00   1.00   12.00    --   82.00  55.00 -36.49   38
  4  \w    103.00 130.00   1.00    3.00    --   70.00  77.00 -59.67   27
  5  \w     92.00 132.00   1.00    3.00    --   62.00  77.00 -94.93   40
  6  \w    108.00 134.00   1.00    3.00    --   70.00  75.00-156.64   26
  7  \w    115.00 152.00   1.00   12.00    --  108.95  77.00 -60.00   37
  8  \w    119.00 176.00   1.00   12.00    --  108.95  77.00   0.00   57
  9  \w    114.00 170.00   1.00   12.00    --  108.95  77.00 -30.00   56
 10  \w     99.00 137.00   1.00    3.00    --   66.00  75.00  92.44   38
 11  \w    103.00 141.00   1.00    3.00    --   70.00  77.00 151.40   38
 12  \w    124.00 155.00   1.00   12.00    --  108.95  61.00 150.00   31
 13  \w     95.00 132.00   1.00    3.00    --   66.00  77.00  49.68   37
 14  \w     95.00 171.00   1.00   12.00    --  108.95 125.00  90.00   76
 15  \w     79.00 105.00   1.00   12.00    --  108.95  77.00 -60.00   26
 16  \w     84.00 110.00   1.00   12.00    --  108.95  61.00 -30.00   26
 17  \w     83.00 110.00   1.00   12.00    --  108.95  61.00   0.00   27
 18  \w     83.00 115.00   1.00   12.00    --  108.95  61.00  30.00   32
 19  \w     84.00 109.00   1.00   12.00    --  108.95  61.00  90.00   25
 20  \w     84.00 139.00   1.00   12.00    --  108.95  61.00 120.00   55
 21  \w     79.00 105.00   1.00   12.00    --  108.95  77.00  90.00   26
 22  \w     83.00 111.00   1.00   12.00    --  108.95  61.00  60.00   28
 23  \w     79.00 105.00   1.00   12.00    --  108.95  77.00 120.00   26
 24  \w     83.00 116.00   1.00   12.00    --  108.95  61.00 150.00   33
 25  \w     79.00 106.00   1.00   12.00    --  108.95  77.00 150.00   27
 26  \w     80.00 178.00   1.00   12.00    --  108.95  77.00  60.00   98
 27  \w     79.00 105.00   1.00   12.00    --  108.95  77.00 -30.00   26
 28  \w     79.00 178.00   1.00   12.00    --  108.95  77.00 -90.00   99
 29  \w     83.00 146.00   1.00   12.00    --  108.95  61.00-180.00   63
 30  \w     79.00 177.00   1.00   12.00    --  108.95  77.00-120.00   98
 31  \w     79.00 160.00   1.00   12.00    --  108.95  77.00  30.00   81
 32  \w     79.00 105.00   1.00   12.00    --  108.95  77.00   0.00   26
 33  \w     55.00  81.00   1.00   12.00    --   82.00  66.00 -77.71   26
 34  \w     49.00  75.00   1.00   12.00    --   78.00  72.00 -99.69   26
 35  \w     40.00  66.00   1.00    3.00    --   70.00  75.00-156.64   26
 36  \w     40.00  68.00   1.00    3.00    --   70.00  76.00-133.64   28
 37  \w     33.00  58.00   1.00    3.00    --   62.00  77.00 -94.93   25
 38  \w     40.00  66.00   1.00    3.00    --   70.00  77.00 -59.67   26
 39  \w     37.00  64.00   1.00    3.00    --   66.00  76.00  19.58   27
 40  \w     36.00  62.00   1.00    3.00    --   66.00  77.00  49.68   26
 41  \w     36.00  66.00   1.00    3.00    --   66.00  75.00  92.44   30
 42  \w     37.00  62.00   1.00    3.00    --   66.00  77.00 135.20   25
 43  \w     40.00  71.00   1.00    3.00    --   70.00  77.00 151.40   31
 44  \w     19.00  44.00   1.00    3.00    --   50.00  80.00 155.71   25
 45  \w      7.00  32.00   1.00    3.00    --   42.00  89.00 165.20   25
 46  \w     18.00  43.00   1.00    3.00    --   50.00  82.00  61.92   25
 47  \w      2.00  27.00   1.00    3.00    --   38.00  90.00 -82.35   25
 48  \w     19.00  46.00   1.00    3.00    --   50.00  81.00 -78.35   27
 49  \w     19.00  44.00   1.00    3.00    --   50.00  81.00-150.39   25
 50  \w     79.00 174.00   1.00   12.00    --  108.95  77.00-180.00   95
 51  \w     79.00 148.00   1.00   12.00    --  108.95  77.00-150.00   69
 52  \w     29.00 108.00   1.00   12.00    --  108.95 -94.00  90.00   79
 53  \w     43.00 139.00   1.00   12.00    --  108.95 -77.00 150.00   96
 54  \w     92.00 121.00   1.00   12.00    --  108.95-125.00 -60.00   29
 55  \w     39.00 113.00   1.00   12.00    --  108.95-125.00  60.00   74
 56  \w     28.00  90.00   1.00    3.00    --   43.31-125.00   0.00   62
 57  \w     23.00  79.00   1.00    3.00    --   43.31-125.00 120.00   56
 58  \w    -43.00  -8.00   1.00    3.00    --  -38.50 -77.00-180.00   35
 59  \w   -107.00 -45.00   1.00    3.00    --  -38.50 -77.00-180.00   62
 60  \w   -107.00 -14.00   1.00    3.00    --  -38.50 -57.00-120.00   93
 61  \w   -110.00 -18.00   1.00    3.00    --  -38.50 -37.00 -30.00   92
 62  \w    -67.00   9.00   1.00    3.00    --  -38.50  77.00-150.00   76
 63  \w   -107.00 -15.00   1.00    3.00    --  -38.50 -57.00  60.00   92
;
_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      0.1057446000
_diffrn_orient_matrix_UB_12      -0.0524122000
_diffrn_orient_matrix_UB_13      0.0204044000
_diffrn_orient_matrix_UB_21      -0.0213047000
_diffrn_orient_matrix_UB_22      -0.0646303000
_diffrn_orient_matrix_UB_23      -0.0334054000
_diffrn_orient_matrix_UB_31      0.0687074000
_diffrn_orient_matrix_UB_32      0.0501379000
_diffrn_orient_matrix_UB_33      -0.0781140000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            62440
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.966
_diffrn_reflns_theta_min         3.669
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.617
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29287
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.477
_exptl_crystal_description       block
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.424
_refine_diff_density_min         -2.115
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1059
_refine_ls_number_reflns         14901
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0501
_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^)+(0.0688P)^2^+5.9505P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1295
_refine_ls_wR_factor_ref         0.1302
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14549
_reflns_number_total             14901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy01617a2.cif
_cod_data_source_block           18062208
_cod_depositor_comments
'Adding full bibliography for 1559569--1559575.cif.'
_cod_database_code               1559569
_chemical_oxdiff_formula         CHNPdClBF
_chemical_oxdiff_usercomment     zhd-C1b
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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
 Cl1-C51
 3 with sigma of 0.02
 C51-Cl1
 2.8 with sigma of 0.02
3. Rigid bond restraints
 F23, F27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F14, F31
 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(F11) \\sim Ueq, Uanis(F32) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(F34) \\sim Ueq, Uanis(F20) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(F36) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F28) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F21) \\sim Ueq, Uanis(F28) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(F27) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F33) = Uanis(F9)
Uanis(F11) = Uanis(F32)
Uanis(F34) = Uanis(F20)
Uanis(F15) = Uanis(F36)
Uanis(F35) = Uanis(F12)
Uanis(F21) = Uanis(F28)
Uanis(F27) = Uanis(F23)
Uanis(Cl1) = Uanis(C38)
5. Others
 Sof(F24)=1-FVAR(1)
 Sof(F25)=FVAR(1)
 Sof(F14)=1-FVAR(2)
 Sof(F31)=FVAR(2)
 Sof(F9)=Sof(F20)=1-FVAR(3)
 Sof(F33)=Sof(F34)=FVAR(3)
 Fixed Sof: Cl1A(0.9) F11(0.4) F12(0.5) F13(0.5) F15(0.5) H35(0.1) H38(0.9)
 H43(0.1) F18(0.4) F19(0.7) F21(0.6) F22(0.5) F23(0.5) Cl1(0.1) Cl2(0.1)
 H48(0.9) Cl2A(0.9) F26(0.5) F27(0.5) F28(0.4) F29(0.3) F30(0.6) F32(0.6)
 F35(0.5) F36(0.5) F37(0.5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C22(H22), C46(H46), C50(H50), C63(H63), C68(H68)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C10(H10), C13(H13), C16(H16), C17(H17), C19(H19), C21(H21),
 C26(H26), C28(H28), C30(H30), C35(H35), C38(H38), C39(H39), C43(H43), C44(H44),
  C45(H45), C51(H51), C53(H53), C54(H54), C57(H57), C58(H58), C59(H59),
 C65(H65), C66(H66)
6.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C67(H67A,H67B,
 H67C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,
 H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,H75B,H75C)
;
_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 2.587
_oxdiff_exptl_absorpt_empirical_full_min 0.538