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_7135271
_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         'C31 H47 B Cl N6 O2 Ti'
_chemical_formula_sum            'C31 H47 B Cl N6 O2 Ti'
_chemical_formula_weight         629.90
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-02-06 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.1780(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8294(2)
_cell_length_b                   15.1747(2)
_cell_length_c                   20.4317(3)
_cell_measurement_reflns_used    12325
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9750
_cell_measurement_theta_min      3.6070
_cell_volume                     3348.68(9)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.960
_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     92.00 117.00   0.50    0.90    --  104.75-125.00  90.00   50
  2  \w     35.00  79.00   0.50    0.90    --  104.75-125.00  90.00   88
  3  \w    -16.00  78.00   0.50    0.13    --   47.05-100.00-110.00  188
  4  \w     34.00 109.00   0.50    0.90    --  104.75-100.00-110.00  150
  5  \w     34.00  62.00   0.50    0.90    --  104.75 -61.00 -60.00   56
  6  \w     47.00  72.00   0.50    0.90    --  104.75 -61.00-120.00   50
  7  \w     37.00  73.00   0.50    0.90    --  104.75 -61.00 -90.00   72
  8  \w     34.00  72.00   0.50    0.90    --  104.75 -61.00  60.00   76
  9  \w    103.00 154.00   0.50    0.90    --  104.75  15.00 150.00  102
 10  \w     96.00 123.00   0.50    0.90    --  104.75 100.00  -5.00   54
 11  \w     79.00 173.00   0.50    0.90    --  104.75 125.00-180.00  188
 12  \w    -61.00 -29.00   0.50    0.90    -- -102.00  61.00-180.00   64
 13  \w   -103.00 -30.00   0.50    0.90    -- -102.00  77.00-180.00  146
 14  \w    -98.00 -39.00   0.50    0.90    -- -102.00  77.00-120.00  118
 15  \w    -69.00 -42.00   0.50    0.90    -- -102.00  61.00 -60.00   54
 16  \w    -14.00  15.00   0.50    0.13    --  -47.05  19.00 -90.00   58
 17  \w    -13.00  28.00   0.50    0.13    --  -47.05  19.00 120.00   82
 18  \w    -62.00 -35.00   0.50    0.90    -- -102.00  61.00 150.00   54
 19  \w   -101.00 -34.00   0.50    0.90    -- -102.00 100.00  -5.00  134
 20  \w    -51.00  23.00   0.50    0.13    --  -47.05 100.00  -5.00  148
 21  \w   -136.00 -84.00   0.50    0.90    -- -102.00-100.00-110.00  104
 22  \w   -110.00 -77.00   0.50    0.13    --  -47.05-125.00   0.00   66
 23  \w   -106.00 -72.00   0.50    0.13    --  -47.05-125.00  30.00   68
;
_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      0.0992389000
_diffrn_orient_matrix_UB_12      0.0514577000
_diffrn_orient_matrix_UB_13      -0.0344735000
_diffrn_orient_matrix_UB_21      0.0844584000
_diffrn_orient_matrix_UB_22      -0.0818465000
_diffrn_orient_matrix_UB_23      0.0037140000
_diffrn_orient_matrix_UB_31      -0.0580344000
_diffrn_orient_matrix_UB_32      -0.0310420000
_diffrn_orient_matrix_UB_33      -0.0671625000
_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  0.0487
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            23283
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.247
_diffrn_reflns_theta_min         3.632
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.183
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52675
_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 light blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       cube
_exptl_crystal_F_000             1340
_exptl_crystal_size_max          0.001
_exptl_crystal_size_mid          0.001
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.469
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         6731
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0706P)^2^+1.2362P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1184
_refine_ls_wR_factor_ref         0.1223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6029
_reflns_number_total             6731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_17761_auto
_cod_database_code               7135271
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti Cl'
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.997
_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:
 C25(H25), C22(H22), B1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C20(H20), C13(H13), C8(H8), C19(H19), C18(H18)
2.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C10(H10A,H10B,H10C), C15(H15A,H15B,H15C), C1(H1A,H1B,H1C),
 C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C24(H24A,H24B,H24C), C11(H11A,H11B,
 H11C), C6(H6A,H6B,H6C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              97528
_shelx_hkl_checksum              192
_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 1.616
_oxdiff_exptl_absorpt_empirical_full_min 0.508