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_1575035
_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         'C22 H30 B2 S2'
_chemical_formula_sum            'C22 H30 B2 S2'
_chemical_formula_weight         380.264
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     direct
_audit_creation_date             2024-05-03
_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                112.891(3)
_cell_angle_beta                 91.006(3)
_cell_angle_gamma                102.222(3)
_cell_formula_units_Z            1
_cell_length_a                   6.4133(7)
_cell_length_b                   8.766(1)
_cell_length_c                   9.6703(11)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      33.06
_cell_measurement_theta_min      2.30
_cell_volume                     486.47(10)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       APEX5
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_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  'olex2.refine 1.5-beta (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9513
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0256
_diffrn_reflns_Laue_measured_fraction_full 0.9994
_diffrn_reflns_Laue_measured_fraction_max 0.9513
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            28911
_diffrn_reflns_point_group_measured_fraction_full 0.9994
_diffrn_reflns_point_group_measured_fraction_max 0.9513
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         33.17
_diffrn_reflns_theta_min         2.30
_diffrn_source                   ImuS-Mo
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.277
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6388
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1188 before and 0.0602 after correction.
The Ratio of minimum to maximum transmission is 0.8557.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       slab
_exptl_crystal_F_000             204.328
_exptl_crystal_recrystallization_method
'The material was recrystallised from chlorobenzene by slow evaporation'
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.5784
_refine_diff_density_min         -0.4715
_refine_diff_density_rms         0.0859
_refine_ls_d_res_high            0.6496
_refine_ls_d_res_low             8.8537
_refine_ls_goodness_of_fit_ref   1.0978
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3539
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.0949
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          -0.0009
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0649P)^2^+0.1940P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1121
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              9
_reflns_limit_h_min              -9
_reflns_limit_k_max              12
_reflns_limit_k_min              -13
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                3117
_reflns_number_total             3539
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc02085a3.cif
_cod_data_source_block           5c
_cod_database_code               1575035
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C9 \\sim H9a: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C7 \\sim H7b: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
2. Rigid body (RIGU) restrains
 C9, H9a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, H7b
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      def2-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-05-03_09-20-59
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mitegen tip NVH oil'
_olex2_submission_original_sample_id MB-Thieno-thiophene-BBN2
_olex2_submission_special_instructions 'No special instructions were received'