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_1575034
_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_absolute_configuration ad
_chemical_formula_moiety         '1(C28 H34 B2 S3)'
_chemical_formula_sum            'C28 H34 B2 S3'
_chemical_formula_weight         488.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-05-06
_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                90
_cell_angle_beta                 94.8085(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.45827(7)
_cell_length_b                   21.26402(19)
_cell_length_c                   18.39205(17)
_cell_measurement_reflns_used    48404
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.5010
_cell_measurement_theta_min      4.7320
_cell_volume                     2516.87(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -84.00   0.00   1.00    7.50    --  -42.75 118.00 176.00   84
  2  \w   -116.00 -55.00   1.00    7.50    --  -42.75-158.00 -63.00   61
  3  \w   -116.00 -55.00   1.00    7.50    --  -42.75-158.00 -63.00   61
  4  \w     22.00  90.00   1.00    7.50    --   42.75-118.00  90.00   68
  5  \w     45.00 119.00   1.00    7.50    --   42.75-158.00 -63.00   74
  6  \w     41.00 110.00   1.00   15.00    --  111.00-118.00  90.00   69
  7  \w     45.00 135.00   1.00   15.00    --  111.00-158.00 -63.00   90
  8  \w     76.00 160.00   1.00   15.00    --  111.00 158.00 -29.00   84
  9  \w    101.00 178.00   1.00   15.00    --  111.00 118.00 176.00   77
 10  \w      2.00  29.00   1.00    7.50    --   38.00  90.00  23.99   27
 11  \w      3.00  31.00   1.00    7.50    --   38.00  87.00-132.29   28
 12  \w   -113.00 -16.00   1.00    7.50    --  -42.75 -57.00-180.00   97
 13  \w   -113.00 -16.00   1.00    7.50    --  -42.75 -57.00-180.00   97
 14  \w   -115.00 -20.00   1.00    7.50    --  -42.75 -38.00  60.00   95
 15  \w   -109.00 -24.00   1.00    7.50    --  -42.75 158.00 -29.00   85
 16  \w     27.00  96.00   1.00    7.50    --   42.75-125.00   0.00   69
 17  \w      6.00  82.00   1.00    7.50    --   42.75 -99.00-180.00   76
 18  \w     20.00 115.00   1.00    7.50    --   42.75  38.00-150.00   95
 19  \w     20.00 115.00   1.00    7.50    --   42.75  38.00-150.00   95
 20  \w     14.00  42.00   1.00    7.50    --   46.00  80.00 101.30   28
 21  \w     14.00  42.00   1.00    7.50    --   46.00  79.00 -49.80   28
 22  \w     23.00 120.00   1.00    7.50    --   50.00  59.00 -91.85   97
 23  \w     23.00 120.00   1.00    7.50    --   50.00  59.00 -91.85   97
 24  \w     24.00 126.00   1.00    7.50    --   54.00  70.00 -53.35  102
 25  \w     24.00 126.00   1.00    7.50    --   54.00  70.00 -53.35  102
 26  \w     24.00 126.00   1.00    7.50    --   54.00  71.00   4.99  102
 27  \w     29.00 129.00   1.00    7.50    --   58.00  69.00 101.57  100
 28  \w     28.00 130.00   1.00    7.50    --   58.00  71.00 178.44  102
 29  \w     28.00 130.00   1.00    7.50    --   58.00  71.00 178.44  102
 30  \w     29.00 129.00   1.00    7.50    --   58.00  69.00 101.57  100
 31  \w     30.00 128.00   1.00    7.50    --   58.00  63.00 -80.42   98
 32  \w     30.00 128.00   1.00    7.50    --   58.00  63.00 -80.42   98
 33  \w     32.00 134.00   1.00    7.50    --   62.00  71.00  50.68  102
 34  \w     32.00 134.00   1.00    7.50    --   62.00  71.00  50.68  102
 35  \w     36.00 138.00   1.00    7.50    --   66.00  71.00 128.77  102
 36  \w     36.00 138.00   1.00    7.50    --   66.00  71.00 128.77  102
 37  \w     36.00 138.00   1.00    7.50    --   66.00  70.00-167.52  102
 38  \w     40.00 142.00   1.00    7.50    --   70.00  71.00  62.73  102
 39  \w     44.00 146.00   1.00    7.50    --   74.00  70.00-156.08  102
 40  \w     44.00 146.00   1.00    7.50    --   74.00  70.00  27.89  102
 41  \w     36.00 135.00   1.00   15.00    --  111.00 -30.00  30.00   99
 42  \w     40.00 135.00   1.00   15.00    --  111.00 -45.00 -90.00   95
 43  \w     83.00 178.00   1.00   15.00    --  111.00  61.00 120.00   95
 44  \w     83.00 178.00   1.00   15.00    --  111.00  61.00 -90.00   95
 45  \w     87.00 178.00   1.00   15.00    --  111.00  45.00  60.00   91
 46  \w     83.00 178.00   1.00   15.00    --  111.00  61.00 120.00   95
 47  \w     90.00 170.00   1.00   15.00    --  111.00  45.00-120.00   80
 48  \w     83.00 110.00   1.00   15.00    --  111.00  61.00   0.00   27
 49  \w    140.00 173.00   1.00   15.00    --  111.00  61.00 -30.00   33
 50  \w    116.00 177.00   1.00   15.00    --  111.00  61.00-180.00   61
 51  \w     83.00 119.00   1.00   15.00    --  111.00  61.00 -30.00   36
 52  \w    140.00 177.00   1.00   15.00    --  111.00  61.00-150.00   37
 53  \w     83.00 110.00   1.00   15.00    --  111.00  61.00-180.00   27
 54  \w     42.00 120.00   1.00   15.00    --  111.00 -61.00  60.00   78
 55  \w     83.00 126.00   1.00   15.00    --  111.00  61.00-150.00   43
 56  \w     84.00 112.00   1.00   15.00    --  111.00-125.00 150.00   28
 57  \w     44.00  69.00   1.00   15.00    --  111.00-125.00 150.00   25
 58  \w     40.00  93.00   1.00   15.00    --  111.00 -77.00-120.00   53
 59  \w    102.00 131.00   1.00   15.00    --  111.00 -77.00-120.00   29
 60  \w     88.00 176.00   1.00   15.00    --  111.00  45.00  90.00   88
 61  \w     89.00 165.00   1.00   15.00    --  111.00  45.00 120.00   76
 62  \w     87.00 173.00   1.00   15.00    --  111.00  45.00  30.00   86
 63  \w     83.00 110.00   1.00   15.00    --  111.00  61.00  90.00   27
 64  \w    132.00 176.00   1.00   15.00    --  111.00  45.00 150.00   44
 65  \w     87.00 127.00   1.00   15.00    --  111.00  45.00 150.00   40
 66  \w     90.00 157.00   1.00   15.00    --  111.00  45.00-180.00   67
 67  \w     89.00 122.00   1.00   15.00    --  111.00  45.00-150.00   33
 68  \w     88.00 162.00   1.00   15.00    --  111.00  45.00 -30.00   74
 69  \w     30.00 107.00   1.00   15.00    --  111.00 -94.00-120.00   77
 70  \w     77.00 134.00   1.00   15.00    --  111.00 -61.00 -60.00   57
 71  \w     81.00 127.00   1.00   15.00    --  111.00 -30.00  30.00   46
 72  \w     87.00 154.00   1.00   15.00    --  111.00  45.00 -60.00   67
 73  \w     88.00 172.00   1.00   15.00    --  111.00  45.00 -90.00   84
 74  \w     43.00 108.00   1.00   15.00    --  111.00-125.00 -60.00   65
 75  \w     83.00 145.00   1.00   15.00    --  111.00  61.00-120.00   62
 76  \w     67.00 127.00   1.00   15.00    --  111.00 -45.00  90.00   60
 77  \w    129.00 156.00   1.00   15.00    --  111.00  61.00  60.00   27
 78  \w    142.00 176.00   1.00   15.00    --  111.00  61.00 -60.00   34
 79  \w     58.00 104.00   1.00   15.00    --  111.00 -94.00 -30.00   46
 80  \w     80.00 115.00   1.00   15.00    --  111.00 -30.00 -90.00   35
 81  \w     83.00 109.00   1.00   15.00    --  111.00  61.00  60.00   26
 82  \w     40.00  69.00   1.00   15.00    --  111.00 -30.00 -90.00   29
 83  \w     76.00 129.00   1.00   15.00    --  111.00 -77.00 -30.00   53
 84  \w    106.00 140.00   1.00   15.00    --  111.00 -77.00  60.00   34
 85  \w     41.00 101.00   1.00   15.00    --  111.00-125.00-120.00   60
 86  \w     83.00 110.00   1.00   15.00    --  111.00  61.00 -60.00   27
 87  \w     48.00  84.00   1.00   15.00    --  111.00 -77.00  60.00   36
 88  \w     93.00 172.00   1.00   15.00    --  111.00  45.00   0.00   79
 89  \w     83.00 110.00   1.00   15.00    --  111.00  61.00  30.00   27
 90  \w     83.00 154.00   1.00   15.00    --  111.00  61.00 150.00   71
 91  \w     31.00 104.00   1.00   15.00    --  111.00 -94.00 -60.00   73
;
_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      -0.0201713000
_diffrn_orient_matrix_UB_12      -0.0497194000
_diffrn_orient_matrix_UB_13      -0.0611323000
_diffrn_orient_matrix_UB_21      0.0253027000
_diffrn_orient_matrix_UB_22      0.0517892000
_diffrn_orient_matrix_UB_23      -0.0571728000
_diffrn_orient_matrix_UB_31      0.2371033000
_diffrn_orient_matrix_UB_32      -0.0097542000
_diffrn_orient_matrix_UB_33      0.0080132000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            97425
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.967
_diffrn_reflns_theta_min         4.158
_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    2.786
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.513
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
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            'translucent dark orange'
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_description       blade
_exptl_crystal_F_000             1040
_exptl_crystal_recrystallization_method
'The material was recrystallised from chlorobenzene by slow evaporation'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.441
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.204(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         10393
_refine_ls_number_restraints     316
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0591P)^2^+0.9885P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0959
_refine_ls_wR_factor_ref         0.0975
_reflns_Friedel_coverage         0.939
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                10035
_reflns_number_total             10393
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02085a3.cif
_cod_data_source_block           5e
_cod_database_code               1575034
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H35 S3'
_chemical_oxdiff_usercomment     '@ 120 K MB-ter-thiophene-BBN2'
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.402
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.796(14)
 0.204(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 C73-C74 \\sim C73-C74A
 with sigma of 0.02
 C73-C80 \\sim C73-C80A
 with sigma of 0.02
 C74-C75 \\sim C74A-C75A
 with sigma of 0.02
 C75-C76 \\sim C75A-C76A
 with sigma of 0.02
 C76-C77 \\sim C76A-C77
 with sigma of 0.02
 C77-C78 \\sim C77-C78A
 with sigma of 0.02
 C78-C79 \\sim C78A-C79A
 with sigma of 0.02
 C79-C80 \\sim C79A-C80A
 with sigma of 0.02
 C73-C75 \\sim C73-C75A
 with sigma of 0.04
 C73-C79 \\sim C73-C79A
 with sigma of 0.04
 C74-C76 \\sim C74A-C76A
 with sigma of 0.04
 C75-C77 \\sim C75A-C77
 with sigma of 0.04
 C77-C79 \\sim C77-C79A
 with sigma of 0.04
 C78-C80 \\sim C78A-C80A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
S52A \\sim C70A \\sim C68A \\sim S53A \\sim C67A \\sim C64A \\sim C69A \\sim
C65A \\sim C71A \\sim C66A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C73 \\sim C77 \\sim C74A \\sim C75A \\sim C76A \\sim C78A \\sim C79A \\sim C80A
\\sim B72: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
5. Rigid body (RIGU) restrains
 S52A, C70A, C68A, S53A, C67A, C64A, C69A, C65A, C71A, C66A, B72, C63
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C73, C77, C74A, C75A, C76A, C78A, C79A, C80A, B72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{S52, S53, C64, C65, C66, C67, C68, C69, C70, C71} sigma for 1-2: 0.01, 1-3:
0.02
as in
{S52A, S53A, C64A, C65A, C66A, C67A, C68A, C69A, C70A, C71A}
7. Others
 Sof(H73A)=Sof(H77A)=Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75C)=
 Sof(H75D)=Sof(C76A)=Sof(H76C)=Sof(H76D)=Sof(C78A)=Sof(H78C)=Sof(H78D)=
 Sof(C79A)=Sof(H79C)=Sof(H79D)=Sof(C80A)=Sof(H80C)=Sof(H80D)=1-FVAR(1)
 Sof(H73)=Sof(H77)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(C79)=Sof(H79A)=
 Sof(H79B)=Sof(C80)=Sof(H80A)=Sof(H80B)=FVAR(1)
 Sof(S52A)=Sof(S53A)=Sof(C64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=
 Sof(C67A)=Sof(C68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=Sof(C71A)=1-FVAR(2)
 Sof(S52)=Sof(S53)=Sof(C64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=
 Sof(C68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=FVAR(2)
8.a Ternary CH refined with riding coordinates:
 C54(H54), C58(H58), C73(H73), C73(H73A), C77(H77), C77(H77A), C4(H4), C8(H8),
 C23(H23), C27(H27)
8.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C55(H55A,H55B), C56(H56A,
 H56B), C57(H57A,H57B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B),
 C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C74A(H74C,H74D), C75A(H75C,
 H75D), C76A(H76C,H76D), C78A(H78C,H78D), C79A(H79C,H79D), C80A(H80C,H80D),
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B), C29(H29A,H29B),
  C30(H30A,H30B)
8.c Aromatic/amide H refined with riding coordinates:
 C61(H61), C62(H62), C65(H65), C66(H66), C69(H69), C70(H70), C65A(H65A),
 C66A(H66A), C69A(H69A), C70A(H70A), C11(H11), C12(H12), C15(H15), C16(H16),
 C19(H19), C20(H20)
;
_shelx_res_checksum              40975
_shelx_hkl_checksum              57783
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder NVH oil'
_olex2_submission_original_sample_id MB-ter-thiophene-BBN2
_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 1.529
_oxdiff_exptl_absorpt_empirical_full_min 0.722