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_7135276
_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         'C38 H60 B2 I2 N14 O2 Ti2, [+ solvents]'
_chemical_formula_sum            'C38 H60 B2 I2 N14 O2 Ti2'
_chemical_formula_weight         1116.22
_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                 95.9910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.93410(10)
_cell_length_b                   15.8235(3)
_cell_length_c                   32.5097(5)
_cell_measurement_reflns_used    17645
_cell_measurement_temperature    156(50)
_cell_measurement_theta_max      75.2170
_cell_measurement_theta_min      3.9150
_cell_volume                     5593.97(15)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      156(50)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.948
_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    -76.00  25.00   0.50    0.36    --  -47.05  92.00  13.00  202
  2  \w    -20.00  66.00   0.50    0.36    --   47.05 -92.00 -99.00  172
  3  \w   -144.00 -81.00   0.50    3.20    -- -102.00 -92.00 -99.00  126
  4  \w    -93.00 -29.00   0.50    3.20    -- -102.00  92.00  13.00  128
  5  \w     71.00 109.00   0.50    3.20    --  104.75 -92.00 -99.00   76
  6  \w    130.00 171.00   0.50    3.20    --  104.75  92.00  13.00   82
  7  \w    -97.00 -71.00   0.50    0.36    --  -47.05-125.00  30.00   52
  8  \w   -103.00 -71.00   0.50    0.36    --  -47.05-125.00  60.00   64
  9  \w    -27.00  26.00   0.50    0.36    --   47.05 -19.00 150.00  106
 10  \w   -112.00 -32.00   0.50    3.20    -- -102.00 125.00  30.00  160
 11  \w    -60.00 -30.00   0.50    3.20    -- -102.00  61.00-150.00   60
 12  \w   -103.00 -29.00   0.50    3.20    -- -102.00  77.00-150.00  148
 13  \w    -66.00 -39.00   0.50    3.20    -- -102.00  61.00 150.00   54
 14  \w   -101.00 -40.00   0.50    3.20    -- -102.00  77.00 -90.00  122
 15  \w     39.00  70.00   0.50    3.20    --  104.75 -61.00 -90.00   62
 16  \w     34.00  71.00   0.50    3.20    --  104.75 -61.00 150.00   74
 17  \w    104.00 178.00   0.50    3.20    --  104.75  30.00 -30.00  148
 18  \w     32.00  58.00   0.50    3.20    --  104.75 -94.00-180.00   52
 19  \w     74.00 101.00   0.50    3.20    --  104.75 -94.00-180.00   54
 20  \w     44.00  69.00   0.50    3.20    --  104.75 -61.00  60.00   50
 21  \w     39.00  71.00   0.50    3.20    --  104.75 -61.00 -60.00   64
 22  \w     42.00  72.00   0.50    3.20    --  104.75 -61.00  90.00   60
;
_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      0.0522230000
_diffrn_orient_matrix_UB_12      -0.0640337000
_diffrn_orient_matrix_UB_13      -0.0293027000
_diffrn_orient_matrix_UB_21      -0.0326592000
_diffrn_orient_matrix_UB_22      0.0603821000
_diffrn_orient_matrix_UB_23      -0.0366941000
_diffrn_orient_matrix_UB_31      0.1275410000
_diffrn_orient_matrix_UB_32      0.0416290000
_diffrn_orient_matrix_UB_33      0.0081529000
_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  0.0447
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            39271
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.417
_diffrn_reflns_theta_min         3.909
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.424
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77071
_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 greenish green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       block
_exptl_crystal_F_000             2248
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.008
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.673
_refine_diff_density_min         -1.214
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     553
_refine_ls_number_reflns         11116
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0539
_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^)+(0.0931P)^2^+3.0703P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8530
_reflns_number_total             11116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04879f2.cif
_cod_data_source_block           exp_17574_auto
_cod_database_code               7135276
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B Ti I'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.894
_reflns_odcompleteness_completeness 99.49
_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:
 C16(H16A,H16B), C19(H19A,H19B), C35(H35A,H35B), C38(H38A,H38B), C18(H18A,
 H18B), C17(H17A,H17B), C37(H37A,H37B), C36(H36A,H36B)
2.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C22(H22), C27(H27), C8(H8), C3(H3), C32(H32)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C34(H34A,H34B,H34C), C10(H10A,H10B,H10C), C29(H29A,H29B,
 H29C), C5(H5A,H5B,H5C), C24(H24A,H24B,H24C), C1(H1A,H1B,H1C), C11(H11A,H11B,
 H11C), C6(H6A,H6B,H6C), C30(H30A,H30B,H30C), C20(H20A,H20B,H20C), C25(H25A,
 H25B,H25C)
;
_shelx_res_checksum              70711
_shelx_hkl_checksum              24826
_shelx_fab_checksum              35128
_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 1.848
_oxdiff_exptl_absorpt_empirical_full_min 0.343