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_1569054
_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         'C30.67 H58.35 B N3 Na O1.67 Si2'
_chemical_formula_sum            'C31 H59 B N3 Na O2 Si2'
_chemical_formula_weight         595.79
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-03-07
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.64110(10)
_cell_length_b                   18.66620(10)
_cell_length_c                   33.6871(2)
_cell_measurement_reflns_used    38757
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.649
_cell_measurement_theta_min      2.692
_cell_volume                     7320.04(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -85.00 -27.00   0.50    0.15    --  -21.00 153.00 -85.00  116
  2  \w    -66.00 -10.00   0.50    0.15    --  -21.00 121.00 115.00  112
  3  \w     32.00  93.00   0.50    0.15    --   47.91-121.00  32.00  122
  4  \w     42.00 110.00   0.50    0.80    --  113.25-121.00  32.00  136
  5  \w     98.00 177.00   0.50    0.80    --  113.25 121.00 115.00  158
  6  \w    -96.00  -7.00   0.50    0.15    --  -21.00 -15.00-180.00  178
  7  \w    -26.00  23.00   0.50    0.15    --   47.91 -19.00  30.00   98
  8  \w    -26.00  23.00   0.50    0.15    --   47.91 -19.00 -60.00   98
  9  \w    -26.00  23.00   0.50    0.15    --   47.91 -19.00  60.00   98
 10  \w     42.00  67.00   0.50    0.80    --  113.25 -61.00  60.00   50
 11  \w     42.00  67.00   0.50    0.80    --  113.25 -61.00 -90.00   50
 12  \w     42.00  67.00   0.50    0.80    --  113.25 -61.00-150.00   50
 13  \w     42.00  67.00   0.50    0.80    --  113.25-125.00 -60.00   50
 14  \w     96.00 139.00   0.50    0.80    --  113.25 125.00   0.00   86
 15  \w     78.00 110.00   0.50    0.80    --  113.25-125.00 -60.00   64
 16  \w     43.00  68.00   0.50    0.80    --  113.25 -61.00  30.00   50
 17  \w     49.00 111.00   0.50    0.80    --  113.25-125.00-120.00  124
 18  \w    101.00 126.00   0.50    0.80    --  113.25  15.00 120.00   50
 19  \w     43.00 106.00   0.50    0.80    --  113.25 -94.00  30.00  126
 20  \w    112.00 162.00   0.50    0.80    --  113.25 125.00 -60.00  100
 21  \w    104.00 157.00   0.50    0.80    --  113.25  77.00 150.00  106
 22  \w     43.00  94.00   0.50    0.80    --  113.25 -94.00-180.00  102
 23  \w     95.00 155.00   0.50    0.80    --  113.25 125.00  60.00  120
 24  \w    146.00 173.00   0.50    0.80    --  113.25 125.00   0.00   54
 25  \w     42.00  67.00   0.50    0.80    --  113.25 -61.00   0.00   50
 26  \w     42.00  67.00   0.50    0.80    --  113.25 -61.00 120.00   50
 27  \w     53.00 102.00   0.50    0.80    --  113.25 -77.00 -60.00   98
 28  \w    101.00 156.00   0.50    0.80    --  113.25  45.00-150.00  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            57708
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.502
_diffrn_reflns_theta_min         4.617
_exptl_absorpt_coefficient_mu    1.210
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.88377
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.081
_exptl_crystal_description       block
_exptl_crystal_F_000             2608
_exptl_crystal_size_max          0.542
_exptl_crystal_size_mid          0.374
_exptl_crystal_size_min          0.317
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.00024(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         7500
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0335P)^2^+4.6065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1074
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7296
_reflns_number_total             7500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01705b2.cif
_cod_data_source_block           21eh054_lb-17-53
_cod_depositor_comments
'Adding full bibliography for 1569049--1569054.cif.'
_cod_database_code               1569054
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.700
_shelx_estimated_absorpt_t_min   0.560
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H5 of C5, H9 of C9, H4 of C4, H2 of C2, H12 of C12, H11
  of C11, H10 of C10, H3 of C3, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H13 of C13, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C21A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.02
3. Others
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=
 Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(N3A)=
 1-FVAR(1)
 Sof(N3)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C31)=
 Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H19C)=Sof(H19D)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C22A)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(Si)=1-FVAR(2)
 Sof(Si2)=Sof(H19A)=Sof(H19B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(2)
 Sof(H13)=1-FVAR(3)
 Sof(O2)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(3)
4.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C19(H19C,H19D), C15(H15A,H15B), C25(H25A,H25B), C26(H26A,
 H26B), C28(H28A,H28B), C29(H29A,H29B), C28A(H28C,H28D), C29A(H29C,H29D)
4.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C5(H5), C9(H9), C4(H4), C2(H2), C10(H10), C3(H3), C12(H12), C11(H11)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C20(H20D,H20E,
 H20F), C27(H27A,H27B,H27C), C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C30(H30A,H30B,H30C),
 C14(H14A,H14B,H14C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C), C30A(H30D,H30E,
 H30F), C31A(H31D,H31E,H31F), C22A(H22D,H22E,H22F), C21A(H21D,H21E,H21F)
;
_shelx_res_checksum              38282
_shelx_hkl_checksum              12137
_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
;