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_7135272
_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         'C62 H94 B2 N14 O4 Ti2'
_chemical_formula_sum            'C62 H94 B2 N14 O4 Ti2'
_chemical_formula_weight         1216.93
_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             2024-02-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-07 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.6860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.5766(2)
_cell_length_b                   14.95160(10)
_cell_length_c                   23.4386(2)
_cell_measurement_reflns_used    32816
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2070
_cell_measurement_theta_min      3.5400
_cell_volume                     7617.19(11)
_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 0.997
_diffrn_measured_fraction_theta_max 0.962
_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     93.00 178.00   0.50    1.00    --  104.75  15.00  60.00  170
  2  \w     89.00 165.00   0.50    1.00    --  104.75 100.00 -56.00  152
  3  \w     92.00 153.00   0.50    1.00    --  104.75  45.00 -90.00  122
  4  \w     48.00  73.00   0.50    1.00    --  104.75 -61.00  30.00   50
  5  \w     47.00  72.00   0.50    1.00    --  104.75 -61.00-120.00   50
  6  \w     33.00  68.00   0.50    1.00    --  104.75 -77.00-150.00   70
  7  \w     32.00  57.00   0.50    1.00    --  104.75 -61.00-180.00   50
  8  \w     36.00  67.00   0.50    1.00    --  104.75 -61.00-150.00   62
  9  \w     78.00 104.00   0.50    1.00    --  104.75 -77.00-150.00   52
 10  \w     34.00  59.00   0.50    1.00    --  104.75 -61.00  90.00   50
 11  \w     58.00 103.00   0.50    1.00    --  104.75 -94.00  30.00   90
 12  \w     34.00  60.00   0.50    0.05    --   46.91-100.00-161.00   52
 13  \w    -20.00   7.00   0.50    0.05    --   46.91-100.00-161.00   54
 14  \w     58.00 110.00   0.50    1.00    --  104.75-100.00-161.00  104
 15  \w    -40.00 -14.00   0.50    0.05    --  -46.91  37.00 120.00   52
 16  \w     -4.00  22.00   0.50    0.05    --  -46.91  37.00 120.00   52
 17  \w    -23.00  15.00   0.50    0.05    --  -46.91  19.00  90.00   76
 18  \w    -24.00  29.00   0.50    0.05    --  -46.91  19.00-150.00  106
 19  \w    -81.00  24.00   0.50    0.05    --  -46.91 100.00 -56.00  210
 20  \w   -100.00 -30.00   0.50    1.00    -- -102.00 100.00 -56.00  140
 21  \w    -62.00 -37.00   0.50    1.00    -- -102.00  61.00 120.00   50
 22  \w    -59.00 -33.00   0.50    1.00    -- -102.00  61.00 150.00   52
 23  \w   -117.00 -78.00   0.50    0.05    --  -46.91-125.00 -30.00   78
 24  \w   -135.00-109.00   0.50    1.00    -- -102.00-100.00-161.00   52
 25  \w   -172.00 -86.00   0.50    1.00    -- -102.00 -94.00-180.00  172
;
_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      -0.0328078000
_diffrn_orient_matrix_UB_12      -0.0315641000
_diffrn_orient_matrix_UB_13      -0.0632271000
_diffrn_orient_matrix_UB_21      0.0298954000
_diffrn_orient_matrix_UB_22      -0.0928759000
_diffrn_orient_matrix_UB_23      0.0141422000
_diffrn_orient_matrix_UB_31      -0.0552639000
_diffrn_orient_matrix_UB_32      -0.0315241000
_diffrn_orient_matrix_UB_33      0.0215123000
_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  0.0398
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            54230
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.389
_diffrn_reflns_theta_min         3.182
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85914
_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 green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       block
_exptl_crystal_F_000             2600
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.722
_refine_diff_density_min         -1.806
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     777
_refine_ls_number_reflns         15364
_refine_ls_number_restraints     799
_refine_ls_restrained_S_all      1.269
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0712
_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^)+(0.1023P)^2^+10.4664P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1957
_refine_ls_wR_factor_ref         0.2001
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14051
_reflns_number_total             15364
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_9147_auto
_cod_database_code               7135272
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.863
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
4.a Ternary CH refined with riding coordinates:
 C53(H53), C56(H56), C25(H25), C22(H22), B2(H2), B1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C62(H62A,H62B), C31(H31A,H31B), C60(H60A,H60B), C61(H61A,
 H61B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C39(H39), C49(H49), C8(H8), C13(H13), C34(H34), C50(H50), C44(H44),
 C51(H51), C20(H20), C18(H18), C19(H19)
4.d Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C10(H10A,H10B,H10C), C41(H41A,H41B,H41C), C5(H5A,H5B,
 H5C), C15(H15A,H15B,H15C), C54(H54A,H54B,H54C), C36(H36A,H36B,H36C), C1(H1A,
 H1B,H1C), C24(H24A,H24B,H24C), C37(H37A,H37B,H37C), C55(H55A,H55B,H55C),
 C11(H11A,H11B,H11C), C57(H57A,H57B,H57C), C26(H26A,H26B,H26C), C6(H6A,H6B,H6C),
  C32(H32A,H32B,H32C), C58(H58A,H58B,H58C), C42(H42A,H42B,H42C), C27(H27A,H27B,
 H27C), C23(H23A,H23B,H23C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20460
_shelx_hkl_checksum              36541
_shelx_fab_checksum              68034
_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 1.201
_oxdiff_exptl_absorpt_empirical_full_min 0.813