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_1569051
_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         'C29 H55 B N3 Na Si2'
_chemical_formula_sum            'C29 H55 B N3 Na Si2'
_chemical_formula_weight         535.74
_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
_audit_creation_date             2020-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-01 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.3580(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.08170(10)
_cell_length_b                   18.6842(2)
_cell_length_c                   16.2208(2)
_cell_measurement_reflns_used    15566
_cell_measurement_temperature    100.3(5)
_cell_measurement_theta_max      76.6680
_cell_measurement_theta_min      3.6010
_cell_volume                     3352.79(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.3(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    -34.00  52.00   1.00    0.50    --  -21.00  47.00 177.00   86
  2  \w    -93.00  -7.00   1.00    0.50    --  -21.00 -47.00  28.00   86
  3  \w    -23.00  50.00   1.00    0.50    --   47.89 -47.00  28.00   73
  4  \w     35.00 121.00   1.00    0.50    --   47.89  47.00 177.00   86
  5  \w     94.00 171.00   1.00    1.00    --  106.80  47.00 177.00   77
  6  \w    -92.00  -8.00   1.00    0.50    --  -21.00 -45.00 150.00   84
  7  \w    -68.00 -12.00   1.00    0.50    --  -21.00 125.00 -90.00   56
  8  \w    -26.00  23.00   1.00    0.50    --   47.89 -19.00-120.00   49
  9  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00  30.00   33
 10  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00 120.00   33
 11  \w     95.00 171.00   1.00    1.00    --  106.80  45.00  90.00   76
 12  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00  90.00   33
 13  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00-120.00   33
 14  \w     35.00 102.00   1.00    1.00    --  106.80 -77.00  90.00   67
 15  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00 150.00   33
 16  \w     35.00 102.00   1.00    1.00    --  106.80 -77.00   0.00   67
 17  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00 -60.00   33
 18  \w     35.00 106.00   1.00    1.00    --  106.80 -94.00-150.00   71
 19  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00   0.00   33
 20  \w     95.00 171.00   1.00    1.00    --  106.80  45.00 -90.00   76
 21  \w     95.00 171.00   1.00    1.00    --  106.80 125.00  30.00   76
 22  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00 -30.00   33
 23  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00 -90.00   33
 24  \w     35.00  68.00   1.00    1.00    --  106.80 -61.00-180.00   33
 25  \w     35.00 102.00   1.00    1.00    --  106.80 -77.00  30.00   67
 26  \w     26.00 121.00   1.00    0.50    --   47.89  77.00   0.00   95
;
_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      -0.1379931000
_diffrn_orient_matrix_UB_12      0.0108112000
_diffrn_orient_matrix_UB_13      -0.0083883000
_diffrn_orient_matrix_UB_21      -0.0139240000
_diffrn_orient_matrix_UB_22      -0.0467182000
_diffrn_orient_matrix_UB_23      0.0771050000
_diffrn_orient_matrix_UB_31      0.0126283000
_diffrn_orient_matrix_UB_32      0.0670849000
_diffrn_orient_matrix_UB_33      0.0550715000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0682
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32490
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.000
_diffrn_reflns_theta_min         3.612
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65117
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.72a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       plate
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.586
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         6931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0806P)^2^+2.0287P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1474
_refine_ls_wR_factor_ref         0.1574
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5830
_reflns_number_total             6931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01705b2.cif
_cod_data_source_block           20EH146_MWS155
_cod_depositor_comments
'Adding full bibliography for 1569049--1569054.cif.'
_cod_database_code               1569051
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C120 H212 B4 N8 Na4 Si8 '
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.828
_diffrn_oxdiff_digest_frames
;
01feacc35055c5b62f8c66d86d515f362a000371bc6
;
_diffrn_oxdiff_digest_hkl
;
0106a8c953b5e480a0a300a22f85f604ea4486
;
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(C26A) = Uanis(C26B) = Uanis(C27A) = Uanis(C27B)
3. Others
 Sof(C27B)=Sof(H27C)=Sof(H27D)=1-FVAR(1)
 Sof(C27A)=Sof(H27A)=Sof(H27B)=FVAR(1)
 Sof(C26B)=Sof(H26C)=Sof(H26D)=1-FVAR(2)
 Sof(C26A)=Sof(H26A)=Sof(H26B)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C7(H7A,H7B), C23(H23A,H23B), C24(H24A,H24B), C26A(H26A,H26B),
 C27A(H27A,H27B), C27B(H27C,H27D), C26B(H26C,H26D)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C2(H2), C15(H15), C16(H16), C19(H19), C5(H5), C4(H4), C3(H3),
 C17(H17), C18(H18)
4.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C22(H22A,H22B,H22C), C12(H12A,H12B,H12C), C9(H9A,H9B,
 H9C), C29(H29A,H29B,H29C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C21(H21A,H21B,
 H21C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              36001
_shelx_hkl_checksum              13429
_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 1.818
_oxdiff_exptl_absorpt_empirical_full_min 0.673