(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_1574128
_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         'C17 H31 Cl2 N Si Ti'
_chemical_formula_sum            'C17 H31 Cl2 N Si Ti'
_chemical_formula_weight         396.29
_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     dual
_audit_creation_date             2022-07-21
_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                93.203(2)
_cell_angle_beta                 92.284(3)
_cell_angle_gamma                95.465(2)
_cell_formula_units_Z            6
_cell_length_a                   6.6617(2)
_cell_length_b                   17.3131(4)
_cell_length_c                   28.1245(10)
_cell_measurement_reflns_used    15839
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      28.2880
_cell_measurement_theta_min      2.5310
_cell_volume                     3220.61(17)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.865
_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    7.00    --   -9.00  11.00-144.00  720
  2  \w    -99.00  81.00   0.25    7.00    --   -9.00  55.00  72.00  720
  3  \w    -99.00  81.00   0.25    7.00    --   -9.00  44.00 -72.00  720
  4  \w    -99.00 -11.25   0.25    7.00    --   -9.00  22.00-180.00  351
;
_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      0.0025480000
_diffrn_orient_matrix_UB_12      0.0020224000
_diffrn_orient_matrix_UB_13      0.0252786000
_diffrn_orient_matrix_UB_21      0.0280342000
_diffrn_orient_matrix_UB_22      0.0405998000
_diffrn_orient_matrix_UB_23      0.0003609000
_diffrn_orient_matrix_UB_31      -0.1033042000
_diffrn_orient_matrix_UB_32      0.0068927000
_diffrn_orient_matrix_UB_33      -0.0004698000
_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  0.0674
_diffrn_reflns_av_unetI/netI     0.0816
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.865
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            49309
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.865
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.260
_diffrn_reflns_theta_min         2.178
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.701
_exptl_absorpt_correction_T_max  0.983
_exptl_absorpt_correction_T_min  0.945
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       plate
_exptl_crystal_F_000             1260
_exptl_crystal_size_max          0.172
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.024
_refine_diff_density_max         0.966
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         15913
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0561
_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^)+(0.0405P)^2^+4.6060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1266
_refine_ls_wR_factor_ref         0.1359
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9764
_reflns_number_total             15913
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00160a2.cif
_cod_data_source_block           TMSCP-Ket_
_cod_depositor_comments
'Adding full bibliography for 1574128--1574129.cif.'
_cod_database_code               1574128
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.889
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A),
 C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B)
2.b 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), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC),
 C10A(H10D,H10E,H10F), C12A(H12D,H12E,H12F), C13A(H13D,H13E,H13F), C14A(H14D,
 H14E,H14F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F),
 C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC), C10B(H10G,H10H,H10I), C12B(H12G,H12H,
 H12I), C13B(H13G,H13H,H13I), C14B(H14G,H14H,H14I), C15B(H15G,H15H,H15I),
 C16B(H16G,H16H,H16I), C17B(H17G,H17H,H17I)
;
_shelx_res_checksum              53222
_shelx_hkl_checksum              65881
_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 2.623
_oxdiff_exptl_absorpt_empirical_full_min 0.591