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_7135274
_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 H43 B Cl N6 O Ti'
_chemical_formula_sum            'C29 H43 B Cl N6 O Ti'
_chemical_formula_weight         585.85
_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             2024-04-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-04-23 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.3540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.73430(10)
_cell_length_b                   21.1361(2)
_cell_length_c                   16.41490(10)
_cell_measurement_reflns_used    15776
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.1610
_cell_measurement_theta_min      4.1800
_cell_volume                     3029.49(5)
_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  (Sheldrick, 2015)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.954
_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    144.00 171.00   0.50    0.20    --  104.75  87.00  70.00   54
  2  \w    148.00 178.00   0.50    0.20    --  104.75  61.00  30.00   60
  3  \w     89.00 131.00   0.50    0.20    --  104.75  61.00  30.00   84
  4  \w    -60.00  19.00   0.50    0.05    --  -46.76  87.00  70.00  158
  5  \w   -128.00 -55.00   0.50    0.20    -- -102.00  87.00  70.00  146
  6  \w   -170.00 -89.00   0.50    0.20    -- -102.00 -45.00  30.00  162
  7  \w   -157.00-125.00   0.50    0.20    -- -102.00 -61.00   0.00   64
  8  \w    -98.00 -72.00   0.50    0.05    --  -46.76-125.00  90.00   52
  9  \w   -109.00 -72.00   0.50    0.05    --  -46.76-125.00  30.00   74
 10  \w   -175.00 -77.00   0.50    0.20    -- -102.00 -87.00 -46.00  196
 11  \w    -69.00 -34.00   0.50    0.20    -- -102.00  61.00-150.00   70
 12  \w    -69.00 -33.00   0.50    0.20    -- -102.00  61.00-180.00   72
 13  \w    -67.00 -30.00   0.50    0.20    -- -102.00  61.00 -90.00   74
 14  \w    -20.00  27.00   0.50    0.05    --  -46.76  19.00-180.00   94
 15  \w    -11.00  16.00   0.50    0.05    --  -46.76  19.00-150.00   54
 16  \w     37.00  64.00   0.50    0.20    --  104.75 -61.00 120.00   54
 17  \w     38.00  65.00   0.50    0.20    --  104.75 -61.00  90.00   54
 18  \w     38.00  72.00   0.50    0.20    --  104.75 -61.00 -30.00   68
 19  \w     35.00  72.00   0.50    0.20    --  104.75 -61.00 -60.00   74
 20  \w     51.00 109.00   0.50    0.20    --  104.75 -94.00-180.00  116
 21  \w    -18.00  73.00   0.50    0.05    --   46.76 -87.00 -46.00  182
 22  \w     43.00  68.00   0.50    0.20    --  104.75 -87.00 -46.00   50
;
_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      -0.0784068000
_diffrn_orient_matrix_UB_12      0.0639526000
_diffrn_orient_matrix_UB_13      0.0160195000
_diffrn_orient_matrix_UB_21      -0.0049795000
_diffrn_orient_matrix_UB_22      0.0137340000
_diffrn_orient_matrix_UB_23      -0.0922103000
_diffrn_orient_matrix_UB_31      -0.1579479000
_diffrn_orient_matrix_UB_32      -0.0321478000
_diffrn_orient_matrix_UB_33      -0.0075397000
_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  0.0305
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20387
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.482
_diffrn_reflns_theta_min         3.410
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.454
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37824
_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 pinkish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       cube
_exptl_crystal_F_000             1244
_exptl_crystal_size_max          0.006
_exptl_crystal_size_mid          0.006
_exptl_crystal_size_min          0.006
_refine_diff_density_max         0.331
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       0.00110(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     365
_refine_ls_number_reflns         6078
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0477P)^2^+1.4837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5758
_reflns_number_total             6078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_15508_auto
_cod_database_code               7135274
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti Cl'
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.980
_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:
 C20(H20), C8(H8), C13(H13), C18(H18), C19(H19), C3(H3)
2.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C27(H27A,H27B,H27C), C25(H25A,H25B,H25C), C15(H15A,H15B,
 H15C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C23(H23A,H23B,H23C), C1(H1A,
 H1B,H1C), C28(H28A,H28B,H28C), C24(H24A,H24B,H24C), C29(H29A,H29B,H29C),
 C5(H5A,H5B,H5C)
;
_shelx_res_checksum              53556
_shelx_hkl_checksum              10298
_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 2.881
_oxdiff_exptl_absorpt_empirical_full_min 0.746