Catalytic Dinitrogen Silylation by Tris(pyrazolyl)borate-Supported Titanium Complexes
Liu, Chenrui; Peng, Lingya; Chen, Yumeng; An, Jingyi; Li, Zhaoxin; Huang, Wenshuang; Cui, Ganglong; Hu, Shaowei; Chemical Communications  (2025) –; doi:10.1039/D5CC04879F

data_7135268
_publ_section_title
;
 Catalytic Dinitrogen Silylation by Tris(pyrazolyl)borate-Supported
 Titanium Complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC04879F
_journal_year                    2025
_chemical_formula_moiety         'C46 H78 B2 N14 O4 Ti2, 0[C6H14]'
_chemical_formula_sum            'C46 H78 B2 N14 O4 Ti2'
_chemical_formula_weight         1008.64
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-07 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.99430(10)
_cell_length_b                   14.99430(10)
_cell_length_c                   29.2000(4)
_cell_measurement_reflns_used    14217
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.3400
_cell_measurement_theta_min      4.1360
_cell_volume                     6565.01(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_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     34.00  69.00   0.50    0.50    --  104.75 -62.00 130.00   70
  2  \w     42.00  70.00   0.50    0.50    --  104.75 -61.00  60.00   56
  3  \w    -21.00  28.00   0.50    0.06    --  -46.66  19.00 150.00   98
  4  \w    -22.00   5.00   0.50    0.06    --  -46.66  62.00 -92.00   54
  5  \w    -61.00 -32.00   0.50    0.50    -- -102.00  60.00  68.00   58
  6  \w    -87.00 -51.00   0.50    0.50    -- -102.00  77.00 120.00   72
  7  \w    -66.00 -29.00   0.50    0.50    -- -102.00  61.00  30.00   74
  8  \w   -100.00 -47.00   0.50    0.50    -- -102.00  77.00 -60.00  106
  9  \w    -68.00 -40.00   0.50    0.50    -- -102.00  62.00 -92.00   56
 10  \w    -59.00 -33.00   0.50    0.50    -- -102.00  61.00-120.00   52
 11  \w    -68.00 -43.00   0.50    0.50    -- -102.00  61.00-150.00   50
 12  \w   -174.00-109.00   0.50    0.50    -- -102.00 -60.00 -71.00  130
 13  \w   -110.00 -72.00   0.50    0.06    --  -46.66-125.00-150.00   76
 14  \w   -117.00 -73.00   0.50    0.06    --  -46.66-125.00  60.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0708898000
_diffrn_orient_matrix_UB_12      0.0158425000
_diffrn_orient_matrix_UB_13      -0.0373350000
_diffrn_orient_matrix_UB_21      -0.0244178000
_diffrn_orient_matrix_UB_22      -0.0997244000
_diffrn_orient_matrix_UB_23      0.0010302000
_diffrn_orient_matrix_UB_31      -0.0703391000
_diffrn_orient_matrix_UB_32      0.0186291000
_diffrn_orient_matrix_UB_33      0.0372643000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            21917
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.592
_diffrn_reflns_theta_min         4.170
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.419
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.020
_exptl_crystal_description       cube
_exptl_crystal_F_000             2152
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.280
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2357 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         6491
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0450P)^2^+4.0167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1025
_refine_ls_wR_factor_ref         0.1041
_reflns_Friedel_coverage         0.694
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.919
_reflns_number_gt                6171
_reflns_number_total             6491
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_10309_auto
_cod_original_cell_volume        6565.01(13)
_cod_database_code               7135268
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 B1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C23(H23a,H23b), C22(H22a,H22b), C20(H20a,H20b), C21(H21a,H21b)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C13(H13), C3(H3)
2.d Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c), C5(H5a,H5b,H5c), C11(H11a,H11b,H11c), C1(H1a,H1b,H1c),
 C18(H18a,H18b,H18c), C15(H15a,H15b,H15c), C6(H6a,H6b,H6c), C19(H19a,H19b,H19c),
  C17(H17a,H17b,H17c)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              35640
_shelx_hkl_checksum              92656
_shelx_fab_checksum              8477
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.507
_oxdiff_exptl_absorpt_empirical_full_min 0.844