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_1559572
_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         '1(C41 H45 Cl3 N2 Pd)'
_chemical_formula_sum            'C41 H45 Cl3 N2 Pd'
_chemical_formula_weight         778.54
_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                89.420(3)
_cell_angle_beta                 76.403(3)
_cell_angle_gamma                88.652(3)
_cell_formula_units_Z            4
_cell_length_a                   11.0716(4)
_cell_length_b                   16.3730(6)
_cell_length_c                   21.6279(7)
_cell_measurement_reflns_used    12049
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.5460
_cell_measurement_theta_min      4.0680
_cell_volume                     3809.6(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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5826
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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    -71.00  33.00   1.00   15.00    --  -36.28  57.00-180.00  104
  2  \w   -124.00 -79.00   1.00   15.00    --  -36.28 -99.00  60.00   45
  3  \w    -50.00 -19.00   1.00   15.00    --  -36.28 -57.00 -30.00   31
  4  \w   -125.00 -50.00   1.00   15.00    --  -36.28-178.00 150.00   75
  5  \w    -58.00 -18.00   1.00   15.00    --  -36.28 -77.00-150.00   40
  6  \w   -105.00   2.00   1.00   15.00    --  -36.28 -77.00 -30.00  107
  7  \w    -68.00  26.00   1.00   15.00    --  -36.28  38.00 120.00   94
  8  \w    -70.00 -41.00   1.00   15.00    --  -36.28 178.00   0.00   29
  9  \w    -40.00 -13.00   1.00   15.00    --  -36.28  38.00 150.00   27
 10  \w   -117.00 -90.00   1.00   15.00    --  -36.28 -99.00 120.00   27
 11  \w     -7.00  23.00   1.00   15.00    --  -36.28  38.00 150.00   30
 12  \w    -93.00 -68.00   1.00   15.00    --  -36.28 -57.00 -30.00   25
 13  \w   -119.00 -81.00   1.00   15.00    --  -36.28 -77.00-150.00   38
 14  \w   -130.00 -86.00   1.00   15.00    --  -36.28 178.00   0.00   44
 15  \w     58.00 112.00   1.00   38.00    --  110.16-111.00-180.00   54
 16  \w    104.00 146.00   1.00   38.00    --  110.16 111.00-180.00   42
 17  \w     35.00 112.00   1.00   38.00    --  110.16-111.00  60.00   77
 18  \w    136.00 174.00   1.00   38.00    --  110.16  45.00 150.00   38
 19  \w     55.00 144.00   1.00   38.00    --  110.16 -45.00  60.00   89
 20  \w     96.00 164.00   1.00   38.00    --  110.16  15.00 -30.00   68
 21  \w     93.00 120.00   1.00   38.00    --  110.16  45.00 150.00   27
 22  \w    118.00 178.00   1.00   38.00    --  110.16  61.00-120.00   60
 23  \w    120.00 152.00   1.00   38.00    --  110.16 -30.00-120.00   32
 24  \w     74.00 100.00   1.00   38.00    --  110.16  61.00-120.00   26
 25  \w     39.00 107.00   1.00   38.00    --  110.16 -77.00-180.00   68
 26  \w     54.00 106.00   1.00   38.00    --  110.16-111.00 -30.00   52
 27  \w     26.00 100.00   1.00   38.00    --  110.16 -30.00-120.00   74
 28  \w     23.00 144.00   1.00   38.00    --  110.16 -77.00-120.00  121
 29  \w     84.00 109.00   1.00   38.00    --  110.16-111.00-120.00   25
 30  \w    116.00 143.00   1.00   38.00    --  110.16 111.00 -30.00   27
 31  \w     22.00  94.00   1.00   38.00    --  110.16 -94.00  90.00   72
 32  \w     24.00  89.00   1.00   38.00    --  110.16  15.00 -30.00   65
;
_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      0.0227541000
_diffrn_orient_matrix_UB_12      -0.0007252000
_diffrn_orient_matrix_UB_13      -0.0730576000
_diffrn_orient_matrix_UB_21      0.0515540000
_diffrn_orient_matrix_UB_22      -0.0883298000
_diffrn_orient_matrix_UB_23      -0.0011146000
_diffrn_orient_matrix_UB_31      -0.1316369000
_diffrn_orient_matrix_UB_32      -0.0324914000
_diffrn_orient_matrix_UB_33      0.0056636000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0733
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            30181
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.885
_diffrn_reflns_theta_min         3.414
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.088
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37880
_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            'metallic dark yellow'
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       plate
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.366
_refine_diff_density_min         -1.358
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1053
_refine_ls_number_reflns         14875
_refine_ls_number_restraints     541
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0688
_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^)+(0.0760P)^2^+11.7223P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1742
_refine_ls_wR_factor_ref         0.1820
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12533
_reflns_number_total             14875
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy01617a2.cif
_cod_data_source_block           18112110_sq
_cod_depositor_comments
'Adding full bibliography for 1559569--1559575.cif.'
_cod_database_code               1559572
_chemical_oxdiff_formula         'C H Cl N Pb'
_chemical_oxdiff_usercomment     C1a
_reflns_odcompleteness_completeness 99.96
_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
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Cl3A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C84) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C86) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C89) \\sim Ueq,
Uanis(C54) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C90) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C70) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C100) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C39)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Pd2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C102) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C83) = Uanis(Cl6A)
Uanis(C1) = Uanis(Cl6)
Uanis(C84) = Uanis(Cl3A)
Uanis(C2) = Uanis(Cl3)
Uanis(C101) = Uanis(C39)
Uanis(C100) = Uanis(C48)
Uanis(C102) = Uanis(C72)
Uanis(C103) = Uanis(C75)
Uanis(C104) = Uanis(C79)
4. Others
 Fixed Sof: C1(0.4) H1A(0.4) H1B(0.4) H1C(0.4) C2(0.5) H2A(0.5) H2B(0.5)
 H2C(0.5) Cl2(0.63494) Cl1(0.63494) Cl3A(0.5) Cl6A(0.4) Cl1A(0.36506)
 Cl2A(0.36506) C39(0.63494) C48(0.63494) H48(0.63494) C54(0.63494)
 H56A(0.63494) H56(0.36506) C61(0.63494) H61(0.63494) C62(0.63494) H62(0.63494)
 C63(0.47051) H64A(0.63494) H64(0.36506) C67(0.63494) H67(0.63494) C69(0.47051)
 H69(0.47051) C70(0.47051) C71(0.47051) H71(0.47051) C72(0.3) H72(0.3)
 C73(0.52949) H73(0.52949) C75(0.7) H75A(0.7) H75B(0.7) H75C(0.7) C76(0.47051)
 H76A(0.47051) H76B(0.47051) H76C(0.47051) C77(0.47051) H77(0.47051)
 C78(0.47051) H78(0.47051) C79(0.3) H79A(0.3) H79B(0.3) H79C(0.3) C80(0.47051)
 H80A(0.47051) H80B(0.47051) H80C(0.47051) C99(0.52949) H99A(0.52949)
 H99B(0.52949) H99C(0.52949) C82(0.47051) H82A(0.47051) H82B(0.47051)
 H82C(0.47051) C83(0.6) H83A(0.6) H83B(0.6) H83C(0.6) Cl6(0.6) C84(0.5)
 H84A(0.5) H84B(0.5) H84C(0.5) Cl3(0.5) C85(0.52949) H85A(0.52949)
 H85B(0.52949) H85C(0.52949) C86(0.36506) C87(0.36506) H87(0.36506)
 C88(0.36506) H88(0.36506) C89(0.36506) H89(0.36506) C90(0.52949) C91(0.47051)
 H91(0.47051) C92(0.52949) H92(0.52949) C93(0.52949) H93(0.52949) C94(0.52949)
 C95(0.52949) H95(0.52949) C96(0.47051) H96A(0.47051) H96B(0.47051)
 H96C(0.47051) C97(0.52949) H97(0.52949) C98(0.52949) H98A(0.52949)
 H98B(0.52949) H98C(0.52949) C81(0.52949) H81A(0.52949) H81B(0.52949)
 H81C(0.52949) C100(0.36506) C101(0.36506) H101(0.36506) C102(0.7) H102(0.7)
 C103(0.3) H10A(0.3) H10B(0.3) H10C(0.3) C104(0.7) H10D(0.7) H10E(0.7) H10F(0.7)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C16(H16), C20(H20), C26(H26), C29(H29),
 C47(H47), C65(H65), C69(H69), C71(H71), C72(H72), C95(H95), C97(H97),
 C102(H102)
5.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C21(H21), C25(H25), C27(H27), C30(H30), C32(H32), C33(H33),
 C36(H36), C40(H40), C43(H43), C48(H48), C49(H49), C50(H50), C56(H56A),
 C56(H56), C57(H57), C60(H60), C61(H61), C62(H62), C64(H64A), C64(H64),
 C66(H66), C67(H67), C73(H73), C77(H77), C78(H78), C87(H87), C88(H88), C89(H89),
  C91(H91), C92(H92), C93(H93), C101(H101)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C34(H34A,H34B,H34C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C55(H55A,H55B,H55C), C59(H59A,H59B,H59C), C68(H68A,H68B,H68C), C74(H74A,
 H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C79(H79A,H79B,H79C),
 C80(H80A,H80B,H80C), C99(H99A,H99B,H99C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C96(H96A,H96B,H96C), C98(H98A,
 H98B,H98C), C81(H81A,H81B,H81C), C103(H10A,H10B,H10C), C104(H10D,H10E,H10F)
;
_shelx_fab_checksum              49788
_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 5.854
_oxdiff_exptl_absorpt_empirical_full_min 0.497