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_7135275
_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         'C30 H48 B N7 O2 Si Ti'
_chemical_formula_sum            'C30 H48 B N7 O2 Si Ti'
_chemical_formula_weight         625.55
_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             2024-02-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                85.0700(10)
_cell_angle_beta                 72.758(2)
_cell_angle_gamma                80.766(2)
_cell_formula_units_Z            2
_cell_length_a                   11.3501(2)
_cell_length_b                   11.8716(2)
_cell_length_c                   13.3789(2)
_cell_measurement_reflns_used    11859
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      75.8080
_cell_measurement_theta_min      3.4710
_cell_volume                     1697.99(5)
_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 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.941
_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    -60.00  24.00   0.50    1.30    --  -47.05  97.00 -30.00  168
  2  \w    -22.00  50.00   0.50    1.30    --   47.05 -97.00-138.00  144
  3  \w    -91.00 -31.00   0.50    4.41    -- -102.00  97.00 -30.00  120
  4  \w   -141.00 -83.00   0.50    4.41    -- -102.00 -97.00-138.00  116
  5  \w     54.00  97.00   0.50    4.41    --  104.75 -97.00-138.00   86
  6  \w     94.00 154.00   0.50    4.41    --  104.75  97.00 -30.00  120
  7  \w    -40.00  19.00   0.50    1.30    --  -47.05  37.00 -30.00  118
  8  \w    -24.00  27.00   0.50    1.30    --  -47.05  19.00-120.00  102
  9  \w   -116.00 -73.00   0.50    1.30    --  -47.05-125.00 -30.00   86
 10  \w    -10.00  17.00   0.50    1.30    --   47.05 -19.00  60.00   54
 11  \w    -23.00  70.00   0.50    1.30    --   47.05 -77.00 150.00  186
 12  \w     89.00 115.00   0.50    1.30    --   47.05  37.00-120.00   52
 13  \w     41.00  66.00   0.50    1.30    --   47.05  37.00-120.00   50
 14  \w   -116.00 -34.00   0.50    4.41    -- -102.00 125.00 -30.00  164
 15  \w   -132.00 -95.00   0.50    4.41    -- -102.00 -45.00 -90.00   74
 16  \w   -117.00 -68.00   0.50    4.41    -- -102.00 125.00 -90.00   98
 17  \w   -174.00-135.00   0.50    4.41    -- -102.00 -45.00 -90.00   78
 18  \w   -165.00 -90.00   0.50    4.41    -- -102.00 -45.00-120.00  150
 19  \w   -106.00 -73.00   0.50    4.41    -- -102.00 125.00   0.00   66
 20  \w    -58.00 -32.00   0.50    4.41    -- -102.00 125.00   0.00   52
 21  \w   -148.00 -88.00   0.50    4.41    -- -102.00 -15.00  60.00  120
 22  \w   -162.00 -89.00   0.50    4.41    -- -102.00 -45.00 -60.00  146
 23  \w    -60.00 -32.00   0.50    4.41    -- -102.00  61.00-150.00   56
 24  \w    141.00 167.00   0.50    4.41    --  104.75  45.00 -90.00   52
 25  \w     33.00  60.00   0.50    4.41    --  104.75 -61.00 120.00   54
 26  \w     90.00 116.00   0.50    4.41    --  104.75-125.00-150.00   52
 27  \w     37.00  63.00   0.50    4.41    --  104.75-125.00-150.00   52
 28  \w     32.00  66.00   0.50    4.41    --  104.75 -94.00  90.00   68
 29  \w    125.00 174.00   0.50    4.41    --  104.75  45.00 -60.00   98
 30  \w     37.00  98.00   0.50    4.41    --  104.75 -94.00  60.00  122
 31  \w     36.00  62.00   0.50    4.41    --  104.75 -94.00 150.00   52
 32  \w     64.00 109.00   0.50    4.41    --  104.75 -94.00 150.00   90
 33  \w     32.00 101.00   0.50    4.41    --  104.75 -77.00-150.00  138
 34  \w     92.00 176.00   0.50    4.41    --  104.75  45.00 120.00  168
 35  \w     72.00 104.00   0.50    4.41    --  104.75 -94.00  90.00   64
 36  \w     35.00  73.00   0.50    4.41    --  104.75 -61.00   0.00   76
;
_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      -0.0034417000
_diffrn_orient_matrix_UB_12      0.1297001000
_diffrn_orient_matrix_UB_13      0.0049325000
_diffrn_orient_matrix_UB_21      0.0854847000
_diffrn_orient_matrix_UB_22      0.0034178000
_diffrn_orient_matrix_UB_23      -0.1133726000
_diffrn_orient_matrix_UB_31      -0.1152953000
_diffrn_orient_matrix_UB_32      0.0219076000
_diffrn_orient_matrix_UB_33      -0.0410224000
_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  0.0290
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       12
_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       -16
_diffrn_reflns_number            19951
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.699
_diffrn_reflns_theta_min         3.462
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.763
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87058
_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 orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.005
_exptl_crystal_size_mid          0.003
_exptl_crystal_size_min          0.002
_refine_diff_density_max         1.616
_refine_diff_density_min         -1.086
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         6727
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0515
_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^)+(0.0735P)^2^+1.1177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1392
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6084
_reflns_number_total             6727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_19070_auto
_cod_database_code               7135275
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti Si'
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.986
_reflns_odcompleteness_completeness 99.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
C26 \\sim C27 \\sim C25 \\sim C24: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
3.a Ternary CH refined with riding coordinates:
 B1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C27(H27A,H27B), C25(H25A,H25B), C26(H26A,H26B)
3.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C8(H8), C3(H3), C18(H18), C20(H20), C19(H19)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C22(H22A,H22B,
 H22C), C11(H11A,H11B,H11C), C00W(H00A,H00B,H00C), C1(H1A,H1B,H1C), C5(H5A,H5B,
 H5C), C010(H01A,H01B,H01C), C013(H01D,H01E,H01F), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              12817
_shelx_hkl_checksum              61849
_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 1.825
_oxdiff_exptl_absorpt_empirical_full_min 0.468