Sodium mediated deprotonative borylation of arenes using sterically demanding B(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>: unlocking polybasic behaviour and competing lateral borane sodiation.
Tortajada, Andreu; Bole, Leonie J.; Mu, Manting; Stanford, Martin; Peñas-Defrutos, Marconi N; García-Melchor, Max; Hevia, Eva; Chemical science 14 (2023) 6538–6545; doi:10.1039/d3sc01705b

data_1569049
_publ_section_title
;
 Sodium mediated deprotonative borylation of arenes using sterically
 demanding B(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>: unlocking
 polybasic behaviour and competing lateral borane sodiation.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              6538
_journal_page_last               6545
_journal_paper_doi               10.1039/d3sc01705b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C28 H63 B N3 Na O Si3'
_chemical_formula_sum            'C28 H63 B N3 Na O Si3'
_chemical_formula_weight         575.88
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-23T18:46:52-00:00
_audit_update_record
;
2023-03-01 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.0050(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.11080(10)
_cell_length_b                   34.6407(2)
_cell_length_c                   11.54530(10)
_cell_measurement_reflns_used    22502
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      77.157
_cell_measurement_theta_min      4.32
_cell_volume                     3749.11(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.66a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.66a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.66a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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    -57.00   0.00   0.50    0.30    --  -18.75 109.00  24.00  114
  2  \w     23.00  88.00   0.50    0.30    --   48.55-109.00 -71.00  130
  3  \w    104.00 171.00   0.50    1.00    --  107.14 109.00  24.00  134
  4  \w     35.00 108.00   0.50    1.00    --  107.14-109.00 -71.00  146
  5  \w    -90.00   5.00   0.50    0.30    --  -18.75 -77.00 -60.00  190
  6  \w    -25.00  23.00   0.50    0.30    --   48.55 -19.00-180.00   96
  7  \w    -22.00  62.00   0.50    0.30    --   48.55 -57.00 -90.00  168
  8  \w    -25.00  23.00   0.50    0.30    --   48.55 -19.00 -90.00   96
  9  \w    -24.00  40.00   0.50    0.30    --   48.55 -38.00 150.00  128
 10  \w    -25.00  23.00   0.50    0.30    --   48.55 -19.00  30.00   96
 11  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00   0.00   54
 12  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00 -90.00   54
 13  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00  30.00   54
 14  \w     85.00 171.00   0.50    1.00    --  107.14  77.00 120.00  172
 15  \w     94.00 171.00   0.50    1.00    --  107.14  38.00  30.00  154
 16  \w     35.00 112.00   0.50    1.00    --  107.14-125.00-150.00  154
 17  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00 -60.00   54
 18  \w     35.00 106.00   0.50    1.00    --  107.14 -99.00   0.00  142
 19  \w     95.00 171.00   0.50    1.00    --  107.14 125.00 -30.00  152
 20  \w     35.00 106.00   0.50    1.00    --  107.14 -99.00  60.00  142
 21  \w     93.00 171.00   0.50    1.00    --  107.14  57.00 -90.00  156
 22  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00 120.00   54
 23  \w     35.00  62.00   0.50    1.00    --  107.14 -57.00  90.00   54
 24  \w     26.00 116.00   0.50    0.30    --   48.55  77.00-180.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0639472
_diffrn_orient_matrix_UB_12      -0.0398144
_diffrn_orient_matrix_UB_13      -0.0081256
_diffrn_orient_matrix_UB_21      0.0721243
_diffrn_orient_matrix_UB_22      0.0172569
_diffrn_orient_matrix_UB_23      -0.0844461
_diffrn_orient_matrix_UB_31      0.1330626
_diffrn_orient_matrix_UB_32      0.0097632
_diffrn_orient_matrix_UB_33      0.1162733
_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  0.0314
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            36567
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.492
_diffrn_reflns_theta_min         2.551
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.437
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.8841
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.40.66a (Rigaku Oxford Diffraction, 2019)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.02
_exptl_crystal_description       plate
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.25
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         7760
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.036
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+0.9218P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0958
_refine_ls_wR_factor_ref         0.1027
_reflns_Friedel_coverage         0
_reflns_number_gt                6627
_reflns_number_total             7760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01705b2.cif
_cod_data_source_block           19EH064_MWS052
_cod_depositor_comments
'Adding full bibliography for 1569049--1569054.cif.'
_cod_database_code               1569049
_shelx_estimated_absorpt_t_min   0.813
_shelx_estimated_absorpt_t_max   0.932
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.886
_shelx_shelxl_version_number     2018/3
_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. Restrained distances
 C9B-C8A \\sim C9A-C8
 with sigma of 0.002
3. Rigid bond restraints
 Si1, C23, C24, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si3, C26, C28, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C32, Si2, C31, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C8A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C4A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C9B)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C7A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
5. Others
 Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C8A)=
 Sof(H8AA)=Sof(H8AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(N6A)=Sof(C5A)=
 Sof(H5AA)=Sof(H5AB)=Sof(N2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(H4AC)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(N2)=Sof(N6)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C12B)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C29(H29A,H29B), C21(H21A,H21B), C5(H5A,H5B), C3(H3A,H3B),
 C8(H8A,H8B), C9A(H9AA,H9AB), C9B(H9BA,H9BB), C8A(H8AA,H8AB), C5A(H5AA,H5AB),
 C3A(H3AA,H3AB)
6.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C7A(H7AA,H7AB,H7AC),
 C4A(H4AA,H4AB,H4AC), C1A(H1AA,H1AB,H1AC)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C17(H17), C15(H15), C16(H16)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C28(H28A,H28B,
 H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C26(H26A,H26B,H26C), C32(H32A,
 H32B,H32C), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C11(H11A,H11B,H11C),
 C12B(H12A,H12B,H12C), C12A(H12D,H12E,H12F)
;
_shelx_res_checksum              25066
_shelx_hkl_checksum              53997