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_7135270
_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         'C27 H39 B Cl N6 O2 Ti'
_chemical_formula_sum            'C27 H39 B Cl N6 O2 Ti'
_chemical_formula_weight         573.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-06 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3620(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.57930(10)
_cell_length_b                   15.3351(2)
_cell_length_c                   18.0389(2)
_cell_measurement_reflns_used    12227
_cell_measurement_temperature    100.1(5)
_cell_measurement_theta_max      75.6500
_cell_measurement_theta_min      3.7720
_cell_volume                     2918.06(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.1(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     33.00  73.00   0.50    0.50    --  104.75 -61.00   0.00   80
  2  \w     36.00  73.00   0.50    0.50    --  104.75 -61.00  60.00   74
  3  \w     40.00  72.00   0.50    0.50    --  104.75 -61.00  90.00   64
  4  \w     36.00  69.00   0.50    0.50    --  104.75 -61.00 120.00   66
  5  \w     85.00 145.00   0.50    0.50    --  104.75 106.00 137.00  120
  6  \w    -27.00  27.00   0.50    0.07    --   46.93 -19.00  90.00  108
  7  \w     33.00  59.00   0.50    0.50    --  104.75 -61.00-120.00   52
  8  \w     32.00  71.00   0.50    0.50    --  104.75 -61.00-180.00   78
  9  \w     66.00 114.00   0.50    0.50    --  104.75-125.00 -90.00   96
 10  \w     58.00 110.00   0.50    0.50    --  104.75-125.00 -30.00  104
 11  \w     50.00 111.00   0.50    0.50    --  104.75-106.00  38.00  122
 12  \w     17.00  81.00   0.50    0.07    --   46.93-106.00  38.00  128
 13  \w    -47.00 -13.00   0.50    0.07    --  -46.93 106.00 137.00   68
 14  \w    -69.00 -35.00   0.50    0.50    -- -102.00 106.00 137.00   68
 15  \w   -101.00 -73.00   0.50    0.50    -- -102.00 106.00 137.00   56
 16  \w    -69.00 -32.00   0.50    0.50    -- -102.00  61.00   0.00   74
 17  \w    -69.00 -29.00   0.50    0.50    -- -102.00  61.00 -30.00   80
 18  \w    -68.00 -29.00   0.50    0.50    -- -102.00  61.00 -60.00   78
 19  \w    -64.00 -30.00   0.50    0.50    -- -102.00  61.00 -90.00   68
 20  \w   -128.00-103.00   0.50    0.50    -- -102.00-106.00  38.00   50
 21  \w   -116.00 -73.00   0.50    0.07    --  -46.93-125.00 120.00   86
 22  \w   -116.00 -73.00   0.50    0.07    --  -46.93-125.00   0.00   86
 23  \w   -114.00 -71.00   0.50    0.07    --  -46.93-125.00 -90.00   86
 24  \w   -116.00 -91.00   0.50    0.07    --  -46.93-125.00-150.00   50
 25  \w   -110.00 -73.00   0.50    0.07    --  -46.93-125.00-180.00   74
 26  \w   -175.00-103.00   0.50    0.50    -- -102.00 -15.00-150.00  144
;
_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      -0.1167794000
_diffrn_orient_matrix_UB_12      0.0043527000
_diffrn_orient_matrix_UB_13      0.0459418000
_diffrn_orient_matrix_UB_21      -0.0168837000
_diffrn_orient_matrix_UB_22      0.0972061000
_diffrn_orient_matrix_UB_23      -0.0199365000
_diffrn_orient_matrix_UB_31      -0.0861023000
_diffrn_orient_matrix_UB_32      -0.0249605000
_diffrn_orient_matrix_UB_33      -0.0694711000
_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  0.0504
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19027
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.788
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.602
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72008
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic pinkish pink'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         5204
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0454
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+1.4907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1189
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4816
_reflns_number_total             5204
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_18761_auto
_cod_database_code               7135270
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti Cl'
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.533
_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:
 C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C13(H13), C8(H8), C20(H20), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C5(H5A,H5B,H5C), C22(H22A,H22B,H22C), C11(H11A,H11B,
 H11C), C23(H23A,H23B,H23C), C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C10(H10A,H10B,
 H10C)
;
_shelx_res_checksum              92793
_shelx_hkl_checksum              34316
_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 1.326
_oxdiff_exptl_absorpt_empirical_full_min 0.632