Ligand non-innocence and an unusual σ-bond metathesis step enables catalytic borylation using 9-borabicyclo-[3.3.1]-nonane
Bisai, Milan Kumar; Łosiewicz, Justyna; Nichol, Gary S.; Dominey, Andrew P.; Thomas, Stephen P.; Macgregor, Stuart A.; Ingleson, Michael J.; Chemical Science 16 (2025) 9255–9263; doi:10.1039/D5SC02085A

data_1575033
_publ_section_title
;
 Ligand non-innocence and an unusual \s-bond metathesis step enables
 catalytic borylation using 9-borabicyclo-[3.3.1]-nonane
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9255
_journal_page_last               9263
_journal_paper_doi               10.1039/D5SC02085A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C24 H32 B2 S2'
_chemical_formula_sum            'C24 H32 B2 S2'
_chemical_formula_weight         406.23
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-04-18
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-17 deposited with the CCDC.	2025-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                116.147(6)
_cell_angle_beta                 98.075(4)
_cell_angle_gamma                99.496(3)
_cell_formula_units_Z            1
_cell_length_a                   6.5122(2)
_cell_length_b                   9.5179(5)
_cell_length_c                   10.1405(7)
_cell_measurement_reflns_used    7454
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.7040
_cell_measurement_theta_min      4.9870
_cell_volume                     540.11(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.81a 64-bit (release 30-01-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2792
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_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    -74.00  32.00   1.00   10.00    --  -42.75  78.00-115.00  106
  2  \w    103.00 178.00   1.00   20.00    --  111.00  78.00-115.00   75
  3  \w     37.00 143.00   1.00   20.00    --  111.00 -78.00 119.00  106
  4  \w   -113.00 -16.00   1.00   10.00    --  -42.75 -57.00  90.00   97
  5  \w    -65.00  30.00   1.00   10.00    --  -42.75  38.00-120.00   95
  6  \w     11.00  42.00   1.00   10.00    --   42.75  77.00 -33.62   31
  7  \w     11.00  42.00   1.00   10.00    --   42.75  79.00  49.00   31
  8  \w     11.00  42.00   1.00   10.00    --   42.75  79.00   0.68   31
  9  \w     11.00  42.00   1.00   10.00    --   42.75  77.00 -11.26   31
 10  \w    -21.00  74.00   1.00   10.00    --   42.75 -78.00 119.00   95
 11  \w     11.00  42.00   1.00   10.00    --   42.75  77.00  76.41   31
 12  \w     20.00 115.00   1.00   10.00    --   42.75  38.00  30.00   95
 13  \w     82.00 178.00   1.00   20.00    --  111.00  69.00  95.91   96
 14  \w     40.00 110.00   1.00   20.00    --  111.00-115.00  28.20   70
 15  \w     39.00 134.00   1.00   20.00    --  111.00 -39.00-108.01   95
 16  \w    103.00 178.00   1.00   20.00    --  111.00  77.00-120.00   75
 17  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00-120.00  105
 18  \w     41.00 139.00   1.00   20.00    --  111.00 -61.00 -90.00   98
 19  \w     66.00 178.00   1.00   20.00    --  111.00  15.00  90.00  112
 20  \w     41.00 112.00   1.00   20.00    --  111.00-125.00-120.00   71
 21  \w    103.00 178.00   1.00   20.00    --  111.00  77.00-150.00   75
 22  \w     41.00 112.00   1.00   20.00    --  111.00-125.00  90.00   71
 23  \w     87.00 175.00   1.00   20.00    --  111.00  30.00 150.00   88
 24  \w    118.00 177.00   1.00   20.00    --  111.00  60.00 161.49   59
 25  \w    147.00 177.00   1.00   20.00    --  111.00  58.00  22.27   30
 26  \w     82.00 108.00   1.00   20.00    --  111.00-108.00 151.11   26
 27  \w     48.00  74.00   1.00   20.00    --  111.00 -94.00  60.00   26
 28  \w     67.00 110.00   1.00   20.00    --  111.00-115.00 -16.26   43
 29  \w     41.00 109.00   1.00   20.00    --  111.00-114.00  96.77   68
 30  \w     42.00 112.00   1.00   20.00    --  111.00-125.00-150.00   70
 31  \w    104.00 176.00   1.00   20.00    --  111.00 125.00 -30.00   72
 32  \w     83.00 134.00   1.00   20.00    --  111.00  68.00 -12.39   51
 33  \w    131.00 176.00   1.00   20.00    --  111.00  30.00 120.00   45
 34  \w     50.00  76.00   1.00   20.00    --  111.00 -77.00  60.00   26
 35  \w     65.00  91.00   1.00   20.00    --  111.00-125.00  60.00   26
 36  \w    145.00 171.00   1.00   20.00    --  111.00 125.00 -60.00   26
 37  \w    138.00 165.00   1.00   20.00    --  111.00  15.00 -30.00   27
 38  \w     93.00 135.00   1.00   20.00    --  111.00 -45.00 150.00   42
 39  \w     53.00  79.00   1.00   20.00    --  111.00 -77.00 -90.00   26
 40  \w     89.00 115.00   1.00   20.00    --  111.00-140.00 -58.92   26
 41  \w     98.00 166.00   1.00   20.00    --  111.00  45.00 150.00   68
 42  \w     88.00 115.00   1.00   20.00    --  111.00  30.00 120.00   27
 43  \w     81.00 106.00   1.00   20.00    --  111.00-125.00  30.00   25
 44  \w     68.00 112.00   1.00   20.00    --  111.00-125.00 150.00   44
 45  \w     84.00 112.00   1.00   20.00    --  111.00-125.00 -60.00   28
 46  \w    108.00 178.00   1.00   20.00    --  111.00  77.00 -90.00   70
 47  \w     76.00 101.00   1.00   20.00    --  111.00 -94.00-180.00   25
 48  \w     69.00  95.00   1.00   20.00    --  111.00-138.00  84.68   26
 49  \w     98.00 123.00   1.00   20.00    --  111.00-138.00  84.68   25
 50  \w    118.00 146.00   1.00   20.00    --  111.00  45.00 -90.00   28
 51  \w     92.00 131.00   1.00   20.00    --  111.00  58.00  22.27   39
 52  \w     49.00  76.00   1.00   20.00    --  111.00-125.00 -60.00   27
 53  \w     83.00 142.00   1.00   20.00    --  111.00  63.00 172.28   59
 54  \w     43.00 110.00   1.00   20.00    --  111.00-115.00-106.02   67
 55  \w     77.00 107.00   1.00   20.00    --  111.00 -94.00-120.00   30
 56  \w     71.00 112.00   1.00   20.00    --  111.00-125.00 -30.00   41
 57  \w     92.00 118.00   1.00   20.00    --  111.00-148.00 114.00   26
 58  \w     89.00 114.00   1.00   20.00    --  111.00  32.00-114.45   25
 59  \w    122.00 148.00   1.00   20.00    --  111.00  32.00-114.45   26
 60  \w    133.00 159.00   1.00   20.00    --  111.00  45.00 -30.00   26
 61  \w    142.00 172.00   1.00   20.00    --  111.00  30.00-150.00   30
 62  \w     64.00  90.00   1.00   20.00    --  111.00 -39.00 130.67   26
 63  \w     98.00 124.00   1.00   20.00    --  111.00 -68.00 -64.18   26
 64  \w     98.00 141.00   1.00   20.00    --  111.00 -77.00  30.00   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1766883000
_diffrn_orient_matrix_UB_12      -0.0756824000
_diffrn_orient_matrix_UB_13      -0.1474930000
_diffrn_orient_matrix_UB_21      0.0460598000
_diffrn_orient_matrix_UB_22      0.1615483000
_diffrn_orient_matrix_UB_23      -0.0047282000
_diffrn_orient_matrix_UB_31      0.1665194000
_diffrn_orient_matrix_UB_32      -0.0543405000
_diffrn_orient_matrix_UB_33      -0.0928892000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5735
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.452
_diffrn_reflns_theta_min         5.006
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.259
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             218
_exptl_crystal_recrystallization_method
'The material was recrystallised from chlorobenzene by slow evaporation'
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.794
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         5735
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0455
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0819P)^2^+0.1203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1300
_refine_ls_wR_factor_ref         0.1330
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5068
_reflns_number_total             5735
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9300\% 
around [-0.00 -0.00 1.00] (reciprocal) or [0.29 0.43 0.85] (direct)
Component 3 rotated by 179.9381\% 
around [-0.00 -0.71 0.71] (reciprocal) or [-0.05 -0.79 0.61] (direct)
;
_cod_data_source_file            d5sc02085a3.cif
_cod_data_source_block           5d
_cod_database_code               1575033
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H19BS
_chemical_oxdiff_usercomment     C16H19BS2
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5774(17)
 0.3006(15) 0.1220(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C5(H5), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
;
_shelx_res_checksum              30145
_shelx_hkl_checksum              20478
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder NVH oil'
_olex2_submission_original_sample_id MB-2,2-Bithiophene-BBN
_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 2.222
_oxdiff_exptl_absorpt_empirical_full_min 0.576
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               3