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_7135269
_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         'C29 H49 B N7 O Si2 Ti'
_chemical_formula_sum            'C29 H49 B N7 O Si2 Ti'
_chemical_formula_weight         626.64
_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             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                79.695(3)
_cell_angle_beta                 71.091(4)
_cell_angle_gamma                65.428(4)
_cell_formula_units_Z            2
_cell_length_a                   11.9183(5)
_cell_length_b                   12.1325(4)
_cell_length_c                   14.2731(6)
_cell_measurement_reflns_used    15512
_cell_measurement_temperature    122(20)
_cell_measurement_theta_max      75.9940
_cell_measurement_theta_min      3.2620
_cell_volume                     1773.34(14)
_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      122(20)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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     31.00 114.00   0.50    0.05    --   47.05  61.00 -65.00  166
  2  \w    138.00 173.00   0.50    0.40    --  104.75  61.00 -65.00   70
  3  \w    109.00 177.00   0.50    0.40    --  104.75  45.00 -30.00  136
  4  \w    102.00 128.00   0.50    0.40    --  104.75  61.00 -65.00   52
  5  \w     96.00 176.00   0.50    0.40    --  104.75  45.00-120.00  160
  6  \w    102.00 156.00   0.50    0.40    --  104.75  30.00  30.00  108
  7  \w     33.00  58.00   0.50    0.40    --  104.75 -61.00 155.00   50
  8  \w     36.00 107.00   0.50    0.40    --  104.75 -77.00 120.00  142
  9  \w     34.00  64.00   0.50    0.40    --  104.75 -61.00  60.00   60
 10  \w     37.00  62.00   0.50    0.40    --  104.75 -61.00  30.00   50
 11  \w     32.00  69.00   0.50    0.40    --  104.75 -61.00 -60.00   74
 12  \w     36.00 106.00   0.50    0.40    --  104.75 -94.00-150.00  140
 13  \w     80.00 115.00   0.50    0.40    --  104.75-125.00-180.00   70
 14  \w     25.00  89.00   0.50    0.05    --   47.05-125.00-180.00  128
 15  \w     76.00 117.00   0.50    0.40    --  104.75-125.00 -90.00   82
 16  \w     40.00 107.00   0.50    0.40    --  104.75 -94.00 -90.00  134
 17  \w     38.00 107.00   0.50    0.40    --  104.75 -94.00 -30.00  138
 18  \w     69.00 107.00   0.50    0.40    --  104.75 -94.00  30.00   76
 19  \w     41.00  78.00   0.50    0.40    --  104.75-125.00  30.00   74
 20  \w     83.00 115.00   0.50    0.40    --  104.75-125.00  30.00   64
 21  \w     38.00 105.00   0.50    0.40    --  104.75-125.00 150.00  134
 22  \w     27.00  64.00   0.50    0.05    --   47.05 -61.00 155.00   74
 23  \w    -49.00 -23.00   0.50    0.05    --  -47.05  61.00 -65.00   52
 24  \w    -17.00   9.00   0.50    0.05    --  -47.05  61.00 -65.00   52
 25  \w    -23.00  21.00   0.50    0.05    --   47.05 -61.00 155.00   88
 26  \w    -25.00   4.00   0.50    0.05    --   47.05 -19.00   0.00   58
 27  \w    -10.00  26.00   0.50    0.05    --  -47.05  37.00 -90.00   72
 28  \w    -66.00 -37.00   0.50    0.40    -- -102.00  61.00 -65.00   58
 29  \w    -68.00 -29.00   0.50    0.40    -- -102.00  61.00 -30.00   78
 30  \w    -68.00 -41.00   0.50    0.40    -- -102.00  61.00  60.00   54
 31  \w    -69.00 -36.00   0.50    0.40    -- -102.00  61.00  90.00   66
 32  \w    -66.00 -29.00   0.50    0.40    -- -102.00  61.00 120.00   74
 33  \w   -175.00-129.00   0.50    0.40    -- -102.00 -30.00  90.00   92
 34  \w   -175.00 -85.00   0.50    0.40    -- -102.00 -61.00 155.00  180
 35  \w   -107.00 -31.00   0.50    0.05    --  -47.05 -61.00 155.00  152
 36  \w    -73.00 -37.00   0.50    0.40    -- -102.00 125.00 -30.00   72
 37  \w   -163.00 -86.00   0.50    0.40    -- -102.00 -61.00-120.00  154
 38  \w   -117.00 -84.00   0.50    0.05    --  -47.05-125.00-150.00   66
 39  \w   -117.00 -91.00   0.50    0.05    --  -47.05-125.00 -60.00   52
;
_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      -0.0858415000
_diffrn_orient_matrix_UB_12      -0.0055583000
_diffrn_orient_matrix_UB_13      -0.0583134000
_diffrn_orient_matrix_UB_21      0.0025018000
_diffrn_orient_matrix_UB_22      0.1194494000
_diffrn_orient_matrix_UB_23      -0.0577594000
_diffrn_orient_matrix_UB_31      0.1205504000
_diffrn_orient_matrix_UB_32      -0.0724354000
_diffrn_orient_matrix_UB_33      -0.0794648000
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20579
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.277
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.936
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74209
_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 orangish orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       block
_exptl_crystal_F_000             670
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     384
_refine_ls_number_reflns         6329
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0387
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+0.3251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1077
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5895
_reflns_number_total             6329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_18759_auto
_cod_database_code               7135269
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti Si'
_shelx_estimated_absorpt_t_max   0.758
_shelx_estimated_absorpt_t_min   0.591
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(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 Aromatic/amide H refined with riding coordinates:
 C13(H13), C8(H8), C26(H26), C3(H3), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C29(H29A,H29B,H29C), C16(H16A,H16B,H16C), C10(H10A,H10B,
 H10C), C15(H15A,H15B,H15C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C1(H1A,H1B,
 H1C), C20(H20A,H20B,H20C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C28(H28A,
 H28B,H28C), C21(H21A,H21B,H21C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              45886
_shelx_hkl_checksum              64848
_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 1.313
_oxdiff_exptl_absorpt_empirical_full_min 0.733