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_1569053
_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         'C27 H61 B N3 Na Si3'
_chemical_formula_sum            'C27 H61 B N3 Na Si3'
_chemical_formula_weight         545.85
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-23T17:34:48-00:00
_audit_update_record
;
2023-03-01 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.481(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5688(15)
_cell_length_b                   17.320(2)
_cell_length_c                   16.3239(10)
_cell_measurement_reflns_used    1361
_cell_measurement_temperature    100.35(10)
_cell_measurement_theta_max      51.507
_cell_measurement_theta_min      5.137
_cell_volume                     3552.4(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.35(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.989
_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    -93.00  -7.00   1.00    0.25    --  -21.00 -52.00  11.00   86
  2  \w    -34.00  52.00   1.00    0.25    --  -21.00  52.00 156.00   86
  3  \w     35.00 121.00   1.00    0.25    --   47.89  52.00 156.00   86
  4  \w    -23.00  56.00   1.00    0.25    --   47.89 -52.00  11.00   79
  5  \w    100.00 171.00   1.00    1.00    --  112.88  52.00 156.00   71
  6  \w     35.00  96.00   1.00    0.25    --   47.89-125.00 -60.00   61
  7  \w    -26.00  23.00   1.00    0.25    --   47.89 -19.00-150.00   49
  8  \w     36.00 121.00   1.00    0.25    --   47.89  38.00-120.00   85
  9  \w     35.00  96.00   1.00    0.25    --   47.89-125.00-150.00   61
 10  \w    100.00 171.00   1.00    1.00    --  112.88  15.00-120.00   71
 11  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00 120.00   26
 12  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00  90.00   26
 13  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00  60.00   26
 14  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00-150.00   26
 15  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00  30.00   26
 16  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00 -90.00   26
 17  \w     97.00 171.00   1.00    1.00    --  112.88  61.00 -90.00   74
 18  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00 -60.00   26
 19  \w     42.00 102.00   1.00    1.00    --  112.88 -77.00-180.00   60
 20  \w     91.00 171.00   1.00    1.00    --  112.88  77.00-120.00   80
 21  \w     42.00 102.00   1.00    1.00    --  112.88 -77.00 -30.00   60
 22  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00-120.00   26
 23  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00   0.00   26
 24  \w    100.00 171.00   1.00    1.00    --  112.88  15.00  30.00   71
 25  \w     42.00 106.00   1.00    1.00    --  112.88 -94.00 120.00   64
 26  \w     42.00 102.00   1.00    1.00    --  112.88 -77.00 120.00   60
 27  \w     42.00  68.00   1.00    1.00    --  112.88 -61.00 150.00   26
 28  \w     97.00 171.00   1.00    1.00    --  112.88  61.00  60.00   74
 29  \w     26.00  86.00   1.00    0.25    --   47.89  77.00 -30.00   60
;
_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      0.1198197
_diffrn_orient_matrix_UB_12      -0.0060548
_diffrn_orient_matrix_UB_13      0.0213195
_diffrn_orient_matrix_UB_21      0.0138993
_diffrn_orient_matrix_UB_22      -0.0564198
_diffrn_orient_matrix_UB_23      -0.0719723
_diffrn_orient_matrix_UB_31      0.0219639
_diffrn_orient_matrix_UB_32      0.0685723
_diffrn_orient_matrix_UB_33      -0.0571908
_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  0.0837
_diffrn_reflns_av_unetI/netI     0.0834
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            33362
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.993
_diffrn_reflns_theta_min         3.722
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.473
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.372
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
        Numerical absorption correction based on gaussian integration over
                        a multifaceted crystal model
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.021
_exptl_crystal_description       prism
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.184
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.108
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.444
_refine_diff_density_rms         0.108
_refine_ls_extinction_coef       0.0007(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         7138
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0875
_refine_ls_R_factor_gt           0.0727
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1039P)^2^+4.8802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1906
_refine_ls_wR_factor_ref         0.2101
_reflns_Friedel_coverage         0
_reflns_number_gt                5803
_reflns_number_total             7138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01705b2.cif
_cod_data_source_block           20EH127_MWS141_2
_cod_depositor_comments
'Adding full bibliography for 1569049--1569054.cif.'
_cod_original_cell_volume        3552.4(7)
_cod_database_code               1569053
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 5.039
_oxdiff_exptl_absorpt_empirical_full_min 0.695
_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. Others
 Sof(Si3B)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C28B)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=Sof(C29B)=Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(1)
 Sof(Si3A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C10(H10A,H10B), C11(H11A,H11B), C15(H15A,H15B), C14(H14A,H14B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C2(H2), C6(H6), C4(H4)
3.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C13(H13A,H13B,H13C), C25(H25A,H25B,
 H25C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C),
 C28A(H28A,H28B,H28C), C29A(H29A,H29B,H29C), C30A(H30A,H30B,H30C), C30B(H30D,
 H30E,H30F), C28B(H28D,H28E,H28F), C29B(H29D,H29E,H29F)
;
_shelx_res_checksum              22258
_shelx_hkl_checksum              38744