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_7135273
_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         'C58 H86 B2 N14 O2 Ti2'
_chemical_formula_sum            'C58 H86 B2 N14 O2 Ti2'
_chemical_formula_weight         1128.82
_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     iterative
_audit_creation_date             2024-04-14
_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                 91.589(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2132(2)
_cell_length_b                   17.9147(3)
_cell_length_c                   26.8010(5)
_cell_measurement_reflns_used    24926
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.0740
_cell_measurement_theta_min      3.3330
_cell_volume                     7301.5(2)
_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    'olex2.solve 1.5 (Bourhis et al., 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 0.987
_diffrn_measured_fraction_theta_max 0.940
_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    -78.00 -53.00   0.50    2.00    --  -46.76 129.00 135.00   50
  2  \w    -85.00 -60.00   0.50    2.00    --  -46.76 141.00 -51.00   50
  3  \w   -103.00 -78.00   0.50    2.00    --  -46.76-129.00  62.00   50
  4  \w   -118.00 -64.00   0.50    2.00    --  -46.76-141.00-109.00  108
  5  \w     46.00  71.00   0.50    2.00    --   46.76-141.00-109.00   50
  6  \w     47.00  96.00   0.50    2.00    --   46.76-129.00  62.00   98
  7  \w   -108.00 -29.00   0.50   12.00    -- -102.00 141.00 -51.00  158
  8  \w   -173.00 -86.00   0.50   12.00    -- -102.00-129.00  62.00  174
  9  \w     83.00 118.00   0.50   12.00    --  104.75-141.00-109.00   70
 10  \w     94.00 120.00   0.50   12.00    --  104.75-129.00  62.00   52
 11  \w     98.00 123.00   0.50   12.00    --  104.75 141.00 -51.00   50
 12  \w   -116.00 -72.00   0.50    2.00    --  -46.76-125.00-180.00   88
 13  \w    -23.00  28.00   0.50    2.00    --  -46.76  19.00-180.00  102
 14  \w    -23.00  29.00   0.50    2.00    --  -46.76  19.00 -90.00  104
 15  \w   -113.00 -71.00   0.50    2.00    --  -46.76-125.00  90.00   84
 16  \w     23.00  49.00   0.50    2.00    --   46.76-125.00-150.00   52
 17  \w   -113.00 -88.00   0.50   12.00    -- -102.00 -15.00 -60.00   50
 18  \w   -174.00-144.00   0.50   12.00    -- -102.00 -15.00 -60.00   60
 19  \w    -98.00 -73.00   0.50   12.00    -- -102.00  77.00 -90.00   50
 20  \w    -66.00 -32.00   0.50   12.00    -- -102.00  61.00-180.00   68
 21  \w    -64.00 -36.00   0.50   12.00    -- -102.00  61.00   0.00   56
 22  \w   -102.00 -77.00   0.50   12.00    -- -102.00  77.00 120.00   50
 23  \w   -172.00 -85.00   0.50   12.00    -- -102.00 -61.00 -30.00  174
 24  \w   -173.00 -89.00   0.50   12.00    -- -102.00 -30.00-120.00  168
 25  \w     36.00 108.00   0.50   12.00    --  104.75 -94.00  60.00  144
 26  \w     46.00  73.00   0.50   12.00    --  104.75 -61.00-150.00   54
 27  \w     39.00 108.00   0.50   12.00    --  104.75 -77.00  60.00  138
 28  \w    121.00 146.00   0.50   12.00    --  104.75  61.00-150.00   50
 29  \w     39.00  72.00   0.50   12.00    --  104.75 -61.00  60.00   66
;
_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      -0.0075436000
_diffrn_orient_matrix_UB_12      -0.0132582000
_diffrn_orient_matrix_UB_13      -0.0568087000
_diffrn_orient_matrix_UB_21      0.0032819000
_diffrn_orient_matrix_UB_22      0.0848617000
_diffrn_orient_matrix_UB_23      -0.0089807000
_diffrn_orient_matrix_UB_31      0.1008988000
_diffrn_orient_matrix_UB_32      -0.0035790000
_diffrn_orient_matrix_UB_33      -0.0023618000
_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  0.0513
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            55802
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.270
_diffrn_reflns_theta_min         3.299
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.201
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78898
_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            'reddish brown'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.027
_exptl_crystal_description       cube
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     727
_refine_ls_number_reflns         14393
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0399P)^2^+9.2636P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1269
_refine_ls_wR_factor_ref         0.1381
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11032
_reflns_number_total             14393
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_16554_auto_sq
_cod_database_code               7135273
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti'
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.40
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 B1(H1), B2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C32(H32), C47(H47), C3(H3), C13(H13), C8(H8), C37(H37), C18(H18),
 C48(H48), C19(H19), C42(H42), C49(H49)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C52(H52A,H52B,H52C), C44(H44A,H44B,
 H44C), C56(H56A,H56B,H56C), C27(H27A,H27B,H27C), C39(H39A,H39B,H39C), C5(H5A,
 H5B,H5C), C34(H34A,H34B,H34C), C10(H10A,H10B,H10C), C53(H53A,H53B,H53C),
 C23(H23A,H23B,H23C), C54(H54A,H54B,H54C), C11(H11A,H11B,H11C), C28(H28A,H28B,
 H28C), C25(H25A,H25B,H25C), C57(H57A,H57B,H57C), C6(H6A,H6B,H6C), C24(H24A,
 H24B,H24C), C30(H30A,H30B,H30C), C40(H40A,H40B,H40C), C1(H1A,H1B,H1C),
 C58(H58A,H58B,H58C), C35(H35A,H35B,H35C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80995
_shelx_hkl_checksum              70571
_shelx_fab_checksum              23862
_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 1.592
_oxdiff_exptl_absorpt_empirical_full_min 0.595