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_7135277
_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         'C54 H78 B2 N14 O4 Ti2'
_chemical_formula_sum            'C54 H78 B2 N14 O4 Ti2'
_chemical_formula_weight         1104.72
_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
_audit_creation_date             2024-02-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-06 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                102.8615(15)
_cell_angle_beta                 110.4311(18)
_cell_angle_gamma                101.9723(18)
_cell_formula_units_Z            2
_cell_length_a                   14.5243(3)
_cell_length_b                   15.2715(3)
_cell_length_c                   20.3140(3)
_cell_measurement_reflns_used    28568
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2400
_cell_measurement_theta_min      3.2820
_cell_volume                     3910.78(15)
_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)'
_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 0.992
_diffrn_measured_fraction_theta_max 0.953
_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    -59.00  21.00   0.50    0.05    --  -46.91  69.00-127.00  160
  2  \w   -111.00 -63.00   0.50    0.05    --  -46.91 -69.00 100.00   96
  3  \w    -15.00  53.00   0.50    0.05    --   46.91 -69.00 100.00  136
  4  \w     41.00 119.00   0.50    0.05    --   46.91  69.00-127.00  156
  5  \w   -164.00 -83.00   0.50    2.00    -- -102.00 -69.00 100.00  162
  6  \w    -80.00 -31.00   0.50    2.00    -- -102.00  69.00-127.00   98
  7  \w     88.00 138.00   0.50    2.00    --  104.75  69.00-127.00  100
  8  \w     32.00  87.00   0.50    2.00    --  104.75 -69.00 100.00  110
  9  \w   -109.00 -81.00   0.50    0.05    --  -46.91-125.00-150.00   56
 10  \w   -114.00 -82.00   0.50    0.05    --  -46.91-125.00   0.00   64
 11  \w     -6.00  28.00   0.50    0.05    --  -46.91  19.00  30.00   68
 12  \w    -94.00 -16.00   0.50    0.05    --  -46.91 125.00-150.00  156
 13  \w    -26.00  22.00   0.50    0.05    --   46.91 -37.00 120.00   96
 14  \w   -135.00 -89.00   0.50    2.00    -- -102.00-125.00 150.00   92
 15  \w   -116.00 -90.00   0.50    2.00    -- -102.00 125.00 -60.00   52
 16  \w   -172.00-143.00   0.50    2.00    -- -102.00-125.00 150.00   58
 17  \w    -60.00 -34.00   0.50    2.00    -- -102.00  61.00  90.00   52
 18  \w    -68.00 -30.00   0.50    2.00    -- -102.00  61.00 150.00   76
 19  \w   -162.00 -78.00   0.50    2.00    -- -102.00-125.00-120.00  168
 20  \w    -82.00 -43.00   0.50    2.00    -- -102.00 125.00 -60.00   78
 21  \w   -175.00-130.00   0.50    2.00    -- -102.00-125.00-150.00   90
 22  \w   -115.00 -71.00   0.50    2.00    -- -102.00-125.00-150.00   88
 23  \w    -66.00 -34.00   0.50    2.00    -- -102.00  61.00 -90.00   64
 24  \w     97.00 135.00   0.50    2.00    --  104.75  45.00  90.00   76
 25  \w    151.00 177.00   0.50    2.00    --  104.75  45.00-180.00   52
 26  \w     49.00  75.00   0.50    2.00    --  104.75-125.00-120.00   52
 27  \w     92.00 138.00   0.50    2.00    --  104.75  45.00-180.00   92
 28  \w     62.00 117.00   0.50    2.00    --  104.75-125.00 120.00  110
 29  \w     36.00  92.00   0.50    2.00    --  104.75-125.00  90.00  112
 30  \w    127.00 161.00   0.50    2.00    --  104.75  15.00 -30.00   68
 31  \w     79.00 177.00   0.50    2.00    --  104.75 125.00  60.00  196
 32  \w     82.00 167.00   0.50    2.00    --  104.75 125.00 150.00  170
 33  \w     70.00 102.00   0.50    2.00    --  104.75 -94.00 150.00   64
 34  \w     32.00 104.00   0.50    2.00    --  104.75 -94.00-180.00  144
 35  \w     55.00 114.00   0.50    2.00    --  104.75-125.00  60.00  118
 36  \w     65.00 106.00   0.50    2.00    --  104.75 -94.00  90.00   82
 37  \w     84.00 109.00   0.50    2.00    --  104.75 -94.00 -30.00   50
 38  \w    152.00 177.00   0.50    2.00    --  104.75  45.00  90.00   50
 39  \w     37.00  62.00   0.50    2.00    --  104.75 -61.00-150.00   50
 40  \w     86.00 117.00   0.50    2.00    --  104.75-125.00-120.00   62
 41  \w     36.00  73.00   0.50    2.00    --  104.75 -61.00-120.00   74
;
_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      -0.1006100000
_diffrn_orient_matrix_UB_12      -0.0101413000
_diffrn_orient_matrix_UB_13      -0.0650802000
_diffrn_orient_matrix_UB_21      0.0339559000
_diffrn_orient_matrix_UB_22      0.1078115000
_diffrn_orient_matrix_UB_23      0.0159162000
_diffrn_orient_matrix_UB_31      0.0540273000
_diffrn_orient_matrix_UB_32      -0.0116808000
_diffrn_orient_matrix_UB_33      -0.0530783000
_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  0.0600
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            50770
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.503
_diffrn_reflns_theta_min         3.278
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.067
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81726
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    0.938
_exptl_crystal_description       cube
_exptl_crystal_F_000             1172
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.465
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         15687
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0693P)^2^+2.3664P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1388
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14256
_reflns_number_total             15687
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_8762_auto_sq
_cod_original_cell_volume        3910.76(14)
_cod_database_code               7135277
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti'
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.904
_reflns_odcompleteness_completeness 99.76
_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.a Ternary CH refined with riding coordinates:
 B1(H1), B2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C51(H27A,H27B), C54(H24A,H24B), C27(H54A,H54B), C24(H51A,H51B), C52(H26A,H52),
  C53(H25A,H25B), C26(H53A,H53B), C25(H52A,H52B)
2.c Aromatic/amide H refined with riding coordinates:
 C40(H8), C13(H35), C35(H13), C18(H47), C30(H3), C8(H30), C47(H18), C20(H45),
 C19(H46), C45(H20), C3(H40), C46(H19)
2.d Idealised Me refined as rotating group:
 C42(H10A,H10B,H10C), C15(H37A,H37B,H37C), C32(H5A,H5B,H5C), C49(H23A,H23B,
 H23C), C11(H33A,H33B,H33C), C37(H15A,H15B,H15C), C5(H42A,H42B,H42C), C10(H32A,
 H32B,H32C), C22(H50A,H50B,H50C), C28(H1A,H1B,H1C), C23(H49A,H49B,H49C),
 C50(H22A,H22B,H22C), C33(H11A,H11B,H11C), C38(H6A,H6B,H6C), C6(H28A,H28B,H28C),
  C1(H38A,H38B,H38C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20888
_shelx_hkl_checksum              14322
_shelx_fab_checksum              62286
_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 1.865
_oxdiff_exptl_absorpt_empirical_full_min 0.297