Unexpected Precatalyst σ-Ligand Effects in Phenoxyimine Zr-Catalyzed Ethylene/1-Octene Copolymerizations.
Gao, Yanshan; Christianson, Matthew D.; Wang, Yang; Chen, Jiazhen; Marshall, Steve; Klosin, Jerzy; Lohr, Tracy L.; Marks, Tobin J.; Journal of the American Chemical Society 141 (2019) 7822–7830; doi:10.1021/jacs.9b01445

data_4128221
_publ_section_title
;
 Unexpected Precatalyst \s-Ligand Effects in Phenoxyimine Zr-Catalyzed
 Ethylene/1-Octene Copolymerizations.
;
_journal_issue                   19
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7822
_journal_page_last               7830
_journal_paper_doi               10.1021/jacs.9b01445
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C40 H66 N2 O2 Zr'
_chemical_formula_sum            'C40 H66 N2 O2 Zr'
_chemical_formula_weight         698.16
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_symmetry_space_group_name_Hall  'P 4cw'
_symmetry_space_group_name_H-M   'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   17.2175(7)
_cell_length_b                   17.2175(7)
_cell_length_c                   41.838(2)
_cell_measurement_reflns_used    9888
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.241
_cell_measurement_theta_min      2.416
_cell_volume                     12402.6(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.02
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0915
_diffrn_reflns_av_unetI/netI     0.0841
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            126771
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.695
_diffrn_reflns_theta_min         0.973
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    0.298
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6475
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1118 before and 0.0790 after correction. The Ratio of minimum to maximum transmission is 0.8688. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_description       plate
_exptl_crystal_F_000             4512
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.093
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.900
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 7455 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.20(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1270
_refine_ls_number_reflns         23461
_refine_ls_number_restraints     1162
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0897
_refine_ls_R_factor_gt           0.0706
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0596P)^2^+37.9068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1616
_refine_ls_wR_factor_ref         0.1717
_reflns_Friedel_coverage         0.971
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                19593
_reflns_number_total             23461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01445_si_003.cif
_cod_data_source_block           cx1318
_cod_original_cell_volume        12402.4(12)
_cod_database_code               4128221
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.973
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6795(17)
 0.3205(17)
2. 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
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Ternary CH refined with riding coordinates:
 C19(H19), C38(H38), C19A(H19A), C38A(H38A), C19B(H19B), C38B(H38B)
4.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C37(H37A,H37B), C18A(H18C,H18D), C37A(H37C,H37D), C18B(H18E,
 H18F), C37B(H37E,H37F)
4.c Me refined with riding coordinates:
 C11A(H11D,H11E,H11F)
4.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C17(H17), C24(H24), C26(H26), C36(H36), C5A(H5A), C7A(H7A),
 C17A(H17A), C24A(H24A), C26A(H26A), C36A(H36A), C5B(H5B), C7B(H7B), C17B(H17B),
  C24B(H24B), C26B(H26B), C36B(H36B)
4.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C1A(H1AA,H1AB,
 H1AC), C2A(H2AA,H2AB,H2AC), C10A(H10D,H10E,H10F), C12A(H12D,H12E,H12F),
 C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C20A(H20D,
 H20E,H20F), C21A(H21D,H21E,H21F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F),
 C31A(H31D,H31E,H31F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F), C35A(H35D,
 H35E,H35F), C39A(H39D,H39E,H39F), C40A(H40D,H40E,H40F), C1B(H1BA,H1BB,H1BC),
 C2B(H2BA,H2BB,H2BC), C10B(H10G,H10H,H10I), C11B(H11G,H11H,H11I), C12B(H12G,
 H12H,H12I), C14B(H14G,H14H,H14I), C15B(H15G,H15H,H15I), C16B(H16G,H16H,H16I),
 C20B(H20G,H20H,H20I), C21B(H21G,H21H,H21I), C29B(H29G,H29H,H29I), C30B(H30G,
 H30H,H30I), C31B(H31G,H31H,H31I), C33B(H33G,H33H,H33I), C34B(H34G,H34H,H34I),
 C35B(H35G,H35H,H35I), C39B(H39G,H39H,H39I), C40B(H40G,H40H,H40I)
;
_shelx_res_checksum              1442
_shelx_hkl_checksum              71069
_olex2_date_sample_data_collection 2018-06-18
_olex2_date_sample_submission    2018-06-17
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1318
_olex2_submission_special_instructions 'No special instructions were received'