(Trialkylsilyl-cyclopentadienyl)titanium(iv) dichloride complexes containing ketimide ligands, Cp′TiCl2(NCtBu2) (Cp′ = Me3SiC5H4, Et3SiC5H4), as efficient catalysts for ethylene copolymerisation with norbornene and tetracyclododecene
Kawatsu, Minaho; Fujioka, Taiga; Losio, Simona; Tritto, Incoronata; Nomura, Kotohiro; Catalysis Science & Technology 15 (2025) 2757–2765; doi:10.1039/D5CY00160A

data_1574129
_publ_section_title
;
 (Trialkylsilyl-cyclopentadienyl)titanium(iv) dichloride complexes
 containing ketimide ligands, Cp&#x2032;TiCl2(N&#xE001;CtBu2) (Cp&#x2032;
 = Me3SiC5H4, Et3SiC5H4), as efficient catalysts for ethylene
 copolymerisation with norbornene and tetracyclododecene
;
_journal_issue                   9
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2757
_journal_page_last               2765
_journal_paper_doi               10.1039/D5CY00160A
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C20 H37 Cl2 N Si Ti'
_chemical_formula_sum            'C20 H37 Cl2 N Si Ti'
_chemical_formula_weight         438.37
_chemical_name_systematic        C20H37Cl2NSiTi
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-01-23
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-05-04 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2674(4)
_cell_length_b                   13.7760(4)
_cell_length_c                   14.0063(4)
_cell_measurement_reflns_used    16728
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      27.9280
_cell_measurement_theta_min      2.6640
_cell_volume                     2367.00(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.937
_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    -99.00  81.00   0.25   20.00    --   -9.00   0.00 -36.00  720
  2  \w    -99.00  81.00   0.25   20.00    --   -9.00  55.00  36.00  720
  3  \w    -98.25  81.00   0.25   20.00    --   -9.00  44.00-108.00  717
  4  \w    -99.00 -14.00   0.25   20.00    --   -9.00   0.00-108.00  340
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0018591000
_diffrn_orient_matrix_UB_12      -0.0500468000
_diffrn_orient_matrix_UB_13      0.0117529000
_diffrn_orient_matrix_UB_21      0.0035707000
_diffrn_orient_matrix_UB_22      -0.0120019000
_diffrn_orient_matrix_UB_23      -0.0491537000
_diffrn_orient_matrix_UB_31      0.0576839000
_diffrn_orient_matrix_UB_32      -0.0008853000
_diffrn_orient_matrix_UB_33      0.0033845000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0774
_diffrn_reflns_av_unetI/netI     0.0677
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            35494
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.184
_diffrn_reflns_theta_min         2.223
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.642
_exptl_absorpt_correction_T_max  0.987
_exptl_absorpt_correction_T_min  0.977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       needle
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.563
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.22(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         5835
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0600P)^2^+0.4209P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1109
_reflns_Friedel_coverage         0.736
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.884
_reflns_number_gt                4384
_reflns_number_total             5835
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00160a2.cif
_cod_data_source_block           TESCP-Ket_
_cod_depositor_comments
'Adding full bibliography for 1574128--1574129.cif.'
_cod_database_code               1574129
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.860
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.78(4)
 0.22(4)
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.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C17(H17A,H17B), C19(H19A,H19B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5)
3.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              17638
_shelx_hkl_checksum              79355
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.799
_oxdiff_exptl_absorpt_empirical_full_min 0.708