Versatile chemistry of six-membered NHC with boranes: bromination at sp3 borane, activation of B–H bond of HBpin, and ring expansion of NHC
Kundu, Gargi; Dixit, Ruchi; Tothadi, Srinu; Vanka, Kumar; Sen, Sakya Singha; Dalton Transactions  (2022) –; doi:10.1039/D2DT01707E

data_7711061
_publ_section_title
;
 Versatile chemistry of six-membered NHC with boranes: bromination at sp3
 borane, activation of B--H bond of HBpin, and ring expansion of NHC
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01707E
_journal_year                    2022
_chemical_formula_moiety         'C28 H41 N2, C12 H8 B O4, C6 H6'
_chemical_formula_sum            'C46 H55 B N2 O4'
_chemical_formula_weight         710.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-07-12
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-06 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 106.590(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   18.245(7)
_cell_length_b                   12.362(5)
_cell_length_c                   18.528(7)
_cell_measurement_reflns_used    9836
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.93
_cell_measurement_theta_min      2.29
_cell_volume                     4005(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Apex3 v2019.11-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 97-2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.951
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0826
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            80481
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.49
_diffrn_reflns_theta_min         2.02
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6110
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1178 before and 0.0650 after correction.
The Ratio of minimum to maximum transmission is 0.8195.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.231
_refine_diff_density_rms         0.045
_refine_ls_extinction_coef       0.0064(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         9657
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0839
_refine_ls_R_factor_gt           0.0544
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0445P)^2^+2.4343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1205
_refine_ls_wR_factor_ref         0.1359
_reflns_number_gt                6979
_reflns_number_total             9657
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d2dt01707e2.cif
_cod_data_source_block           mo_gk_bcat_0ma_a
_cod_database_code               7711061
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  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:
 C19(H19), C26(H26), C38(H38), C35(H35)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C2(H2), C8(H8), C10(H10), C3(H3), C5(H5), C9(H9), C4(H4), C17(H17),
 C33(H33), C31(H31), C22(H22), C32(H32), C21(H21), C23(H23), C45(H45), C43(H43),
  C46(H46), C42(H42), C44(H44), C41(H41)
2.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C28(H28A,H28B,
 H28C), C37(H37A,H37B,H37C), C27(H27A,H27B,H27C), C36(H36A,H36B,H36C), C39(H39A,
 H39B,H39C)
;
_olex2_submission_special_instructions 'No special instructions were received'