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_1575037
_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         'C37 H57 B N2 Zn, C6 H6'
_chemical_formula_sum            'C43 H63 B N2 Zn'
_chemical_formula_weight         690.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-20
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-01-17 deposited with the CCDC.	2025-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.123(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7925(4)
_cell_length_b                   24.0811(7)
_cell_length_c                   13.5539(5)
_cell_measurement_reflns_used    9847
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      32.16
_cell_measurement_theta_min      2.37
_cell_volume                     3990.3(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       APEX4
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.9990
_diffrn_measured_fraction_theta_max 0.9963
_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  0.0479
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 0.9990
_diffrn_reflns_Laue_measured_fraction_max 0.9963
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            242361
_diffrn_reflns_point_group_measured_fraction_full 0.9990
_diffrn_reflns_point_group_measured_fraction_max 0.9963
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         33.19
_diffrn_reflns_theta_min         2.10
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.646
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.7204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0600 before and 0.0496 after correction.
The Ratio of minimum to maximum transmission is 0.9650.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       block
_exptl_crystal_F_000             1482.038
_exptl_crystal_recrystallization_method
'The material was recrystallised from d6-benzene by slow evaporation'
_exptl_crystal_size_max          0.145
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.4086
_refine_diff_density_min         -0.4803
_refine_diff_density_rms         0.0718
_refine_ls_d_res_high            0.6492
_refine_ls_d_res_low             9.6870
_refine_ls_goodness_of_fit_ref   1.0862
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    1
_refine_ls_number_parameters     1082
_refine_ls_number_reflns         15206
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.0827
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+0.4221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0297
_refine_ls_wR_factor_ref         0.0335
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -19
_reflns_limit_k_max              37
_reflns_limit_k_min              0
_reflns_limit_l_max              20
_reflns_limit_l_min              -11
_reflns_number_gt                12154
_reflns_number_total             15206
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc02085a3.cif
_cod_data_source_block           11
_cod_database_code               1575037
_olex2_refinement_description
;
1. Restrained distances
 C23-C27 \\sim C23-C27A
 with sigma of 0.02
 C27-C29 \\sim C27A-C29A
 with sigma of 0.02
 C23-C29 \\sim C23-C29A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C28-C29 \\sim C28A-C29A
 with sigma of 0.04
 C23-C28 \\sim C23-C28A
 with sigma of 0.04
2. Rigid body (RIGU) restrains
 C27, C28, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27A, C28A, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29A, H29d, H29f, H29e
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 H29b, C29, H29c, H29d
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28, H28c, H28b, H28a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28A, H28d, H28f, H28e
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28d)=Sof(H28e)=Sof(H28f)=Sof(C29A)=
 Sof(H29d)=Sof(H29e)=Sof(H29f)=1-FVAR(1)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28a)=Sof(H28b)=Sof(H28c)=Sof(C29)=Sof(H29a)=
 Sof(H29b)=Sof(H29c)=FVAR(1)
;
_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_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:           2023-03-17_15-45-28
;
_olex2_submission_original_sample_id MB-LZnH-HBBN
_olex2_submission_special_instructions 'No special instructions were received'