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_1575036
_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         'C29 H48 B3 N'
_chemical_formula_sum            'C29 H48 B3 N'
_chemical_formula_weight         443.184
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_Int_Tables_number      62
_atom_sites_solution_primary     direct
_audit_creation_date             2024-05-16
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5001(5)
_cell_length_b                   15.0759(5)
_cell_length_c                   12.6679(5)
_cell_measurement_reflns_used    9866
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      36.12
_cell_measurement_theta_min      2.59
_cell_volume                     2578.25(16)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       APEX5
_computing_data_reduction        'SAINT V8.40B (?, 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 0.9988
_diffrn_measured_fraction_theta_max 0.9977
_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  0.0475
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 0.9988
_diffrn_reflns_Laue_measured_fraction_max 0.9977
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            232973
_diffrn_reflns_point_group_measured_fraction_full 0.9988
_diffrn_reflns_point_group_measured_fraction_max 0.9977
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         36.36
_diffrn_reflns_theta_min         2.59
_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    0.063
_exptl_absorpt_correction_T_max  0.7471
_exptl_absorpt_correction_T_min  0.7184
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1062 before and 0.0553 after correction.
The Ratio of minimum to maximum transmission is 0.9616.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       block
_exptl_crystal_F_000             976.440
_exptl_crystal_recrystallization_method
'The material was recrystallised from d2-dichloromethane by slow evaporation'
_exptl_crystal_size_max          0.575
_exptl_crystal_size_mid          0.425
_exptl_crystal_size_min          0.294
_refine_diff_density_max         0.3395
_refine_diff_density_min         -0.1990
_refine_diff_density_rms         0.0385
_refine_ls_d_res_high            0.5994
_refine_ls_d_res_low             7.8767
_refine_ls_goodness_of_fit_ref   1.1684
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     388
_refine_ls_number_reflns         6441
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.1684
_refine_ls_R_factor_all          0.0301
_refine_ls_R_factor_gt           0.0199
_refine_ls_shift/su_max          -0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0081P)^2^+0.1103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0349
_refine_ls_wR_factor_ref         0.0388
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              22
_reflns_limit_h_min              0
_reflns_limit_k_max              25
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                5450
_reflns_number_total             6441
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc02085a3.cif
_cod_data_source_block           3j-[H-BBN]
_cod_database_code               1575036
_olex2_refinement_description
;
;
_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:      cc-pVTZ
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-05-15_14-31-33
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in paratone oil'
_olex2_submission_original_sample_id JL-136
_olex2_submission_special_instructions 'No special instructions were received'