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_4128225
_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         'C38 H60 Cl2 N2 O2 Zr, 2(C7 H8)'
_chemical_formula_sum            'C52 H76 Cl2 N2 O2 Zr'
_chemical_formula_weight         923.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.221(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   34.428(4)
_cell_length_b                   7.6685(8)
_cell_length_c                   20.142(2)
_cell_measurement_reflns_used    9926
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.174
_cell_measurement_theta_min      4.492
_cell_volume                     5197.2(10)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            32616
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.168
_diffrn_reflns_theta_min         4.492
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    2.960
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6351
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1188 before and 0.0386 after correction.
The Ratio of minimum to maximum transmission is 0.8433.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.180
_exptl_crystal_description       block
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.226
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.900
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         4716
_refine_ls_number_restraints     380
_refine_ls_restrained_S_all      1.187
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0349P)^2^+8.8972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0827
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4482
_reflns_number_total             4716
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01445_si_004.cif
_cod_data_source_block           cx0255a
_cod_original_cell_volume        5197.2(9)
_cod_database_code               4128225
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.554
_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
 C3A-C2 \\sim C3-C2 \\sim C4A-C3A \\sim C4-C3 \\sim C5-C4 \\sim C5A-C4A \\sim
C6-C5A \\sim C6-C5
 with sigma of 0.01
 C12A-C11A \\sim C12-C11 \\sim C13-C11 \\sim C13A-C11A \\sim C14A-C11A \\sim
C14-C11
 with sigma of 0.01
3. Rigid bond restraints
 C3, C3A, C4, C4A, C5, C5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C20, C21, C22, C23, C24, C25, C20A, C21A, C22A, C23A, C24A, C25A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C11A, C12, C12A, C13, C13A, C14, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C26, C26B, C26A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3 \\sim C3A \\sim C4 \\sim C4A \\sim C5 \\sim C5A: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim C24A \\sim C25A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C11 \\sim C11A \\sim C12 \\sim C12A \\sim C13 \\sim C13A \\sim C14 \\sim C14A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C26 \\sim C26B \\sim C26A: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C3A) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.02
5. Others
 1*[Sof(C26B)+Sof(H26D)+Sof(H26E)+Sof(H26F)]+1*[Sof(C26)+Sof(H26A)+Sof(H26B)+
 Sof(H26C)]+1*[Sof(C26A)+Sof(H26G)+Sof(H26H)+Sof(H26I)]=1 with esd of 0.0001
 Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=
 Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=1-FVAR(1)
 Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=
 Sof(H24)=Sof(C25)=FVAR(1)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C11A)=Sof(C12A)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=
 Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=Sof(H5)=Sof(C11)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(2)
 Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=FVAR(3)
 Sof(C26A)=Sof(H26G)=Sof(H26H)=Sof(H26I)=FVAR(4)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C17(H17)
6.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
6.c Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C26A(H26G,H26H,H26I)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C3A(H3A), C5(H5), C5A(H5A), C15(H15), C21(H21), C22(H22), C23(H23),
 C24(H24), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A)
6.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C12A(H12D,H12E,H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,
 H14C), C14A(H14D,H14E,H14F), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              42916
_shelx_hkl_checksum              42028
_olex2_date_sample_data_collection 2015-02-04
_olex2_date_sample_submission    2015-01-29
_olex2_submission_original_sample_id cx0255a
_olex2_submission_special_instructions 'No special instructions were received'