Surface vs Homogeneous Organo-Hafnium Catalyst Ion-Pairing and Ligand Effects on Ethylene Homo- and Copolymerizations
Zhang, Jialong; Mason, Alexander H.; Motta, Alessandro; Cesar, Laryssa G.; Kratish, Yosi; Lohr, Tracy L.; Miller, Jeffrey T.; Gao, Yanshan; Marks, Tobin J.; ACS Catalysis  (2021) 3239–3250; doi:10.1021/acscatal.0c04678

data_4518510
_publ_section_title
;
 Surface vs Homogeneous Organo-Hafnium Catalyst Ion-Pairing and Ligand
 Effects on Ethylene Homo- and Copolymerizations
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              3239
_journal_page_last               3250
_journal_paper_doi               10.1021/acscatal.0c04678
_journal_year                    2021
_chemical_formula_moiety         'C30 H42 Hf N2'
_chemical_formula_sum            'C30 H42 Hf N2'
_chemical_formula_weight         609.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-08-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.23 svn.r3337 for OlexSys, GUI svn.r5217)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.416(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.2803(12)
_cell_length_b                   9.5964(6)
_cell_length_c                   33.993(2)
_cell_measurement_reflns_used    9853
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.256
_cell_measurement_theta_min      2.357
_cell_volume                     5636.9(6)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.82
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.680
_diffrn_measured_fraction_theta_max 0.825
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.2196
_diffrn_reflns_Laue_measured_fraction_full 0.680
_diffrn_reflns_Laue_measured_fraction_max 0.825
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            94890
_diffrn_reflns_point_group_measured_fraction_full 0.680
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.564
_diffrn_reflns_theta_min         1.674
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    3.720
_exptl_absorpt_correction_T_max  0.6802
_exptl_absorpt_correction_T_min  0.5823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0803 before and 0.0470 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1178 before and 0.0604 after correction.
 The Ratio of minimum to maximum transmission is 0.84.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 49481 reflections, Rint = 0.0560
 (26422 with I > 3sig(I), Rint = 0.0443)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       needle
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.028
_refine_diff_density_max         1.430
_refine_diff_density_min         -1.473
_refine_diff_density_rms         0.267
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         6945
_refine_ls_number_restraints     558
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.1411
_refine_ls_R_factor_gt           0.0949
_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^)+(0.0799P)^2^+305.3650P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2218
_refine_ls_wR_factor_ref         0.2365
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4785
_reflns_number_total             6945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04678_si_001.cif
_cod_data_source_block           cx0832_a
_cod_original_cell_volume        5636.8(6)
_cod_database_code               4518510
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.653
_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. 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
3.a Ternary CH refined with riding coordinates:
 C9(H9), C16(H16), C25(H25), C28(H28), C9A(H9A), C16A(H16A), C25A(H25A),
 C28A(H28A)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14), C15(H15),
 C21(H21), C22(H22), C23(H23), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A),
 C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A), C21A(H21A), C22A(H22A),
 C23A(H23A)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C1A(H1AA,H1AB,H1AC), C2A(H2AA,H2AB,H2AC), C3A(H3AA,
 H3AB,H3AC), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C26A(H26D,H26E,H26F),
 C27A(H27D,H27E,H27F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
;
_shelx_res_checksum              750
_shelx_hkl_checksum              85816
_olex2_date_sample_data_collection 2016-08-23
_olex2_date_sample_submission    2016-08-16
_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 cx0832
_olex2_submission_special_instructions 'No special instructions were received'