Hexamethylbenzene elimination enables the generation of transient, sterically unhindered multiply bonded boron species
Zhang, Chonghe; Dabringhaus, Philipp; Tra, Bi Youan E.; Gilliard, Robert J.; Cummins, Christopher C.; Chemical Science 16 (2025) 11841–11848; doi:10.1039/D5SC02645H

data_1574656
_publ_section_title
;
 Hexamethylbenzene elimination enables the generation of transient,
 sterically unhindered multiply bonded boron species
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              11841
_journal_page_last               11848
_journal_paper_doi               10.1039/D5SC02645H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C45 H32 B2 F15 N, C27 H32 B N'
_chemical_formula_sum            'C72 H64 B3 F15 N2'
_chemical_formula_weight         1274.68
_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   mixed
_audit_creation_date             2023-10-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-10 deposited with the CCDC.	2025-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                92.077(8)
_cell_angle_beta                 107.094(8)
_cell_angle_gamma                109.231(7)
_cell_formula_units_Z            2
_cell_length_a                   13.063(3)
_cell_length_b                   15.942(3)
_cell_length_c                   21.120(5)
_cell_measurement_reflns_used    9124
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      31.57
_cell_measurement_theta_min      2.28
_cell_volume                     3926.0(15)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0762
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            337344
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.089
_diffrn_reflns_theta_min         2.040
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.7252
_exptl_absorpt_correction_T_min  0.6680
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1150 before and 0.0870 after correction.
The Ratio of minimum to maximum transmission is 0.9211.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.078
_exptl_crystal_description       plate
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.411
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1015
_refine_ls_number_reflns         27270
_refine_ls_number_restraints     328
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0920
_refine_ls_R_factor_gt           0.0713
_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^)+(0.0720P)^2^+2.0878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1747
_refine_ls_wR_factor_ref         0.1897
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20017
_reflns_number_total             27270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02645h3.cif
_cod_data_source_block           5and6
_cod_depositor_comments
'Adding full bibliography for 1574650--1574657.cif.'
_cod_original_cell_volume        3925.8(16)
_cod_database_code               1574656
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.980
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N018-C01S \\sim N0-C01S
 with sigma of 0.02
 N00I-C00V \\sim N00J-C00V
 with sigma of 0.02
 N018-C01V \\sim N0-C1
 with sigma of 0.02
 N00I-C021 \\sim N00J-C8
 with sigma of 0.02
 C01V-C01W \\sim C1-C2
 with sigma of 0.02
 N00I-C02D \\sim N00J-C9
 with sigma of 0.04
 C01V-C026 \\sim C1-C3
 with sigma of 0.02
 N00I-C02F \\sim N00J-C10
 with sigma of 0.04
 C01W-C022 \\sim C2-C0
 with sigma of 0.02
 C01W-C02A \\sim C2-C5
 with sigma of 0.02
 C026-C02B \\sim C3-C7
 with sigma of 0.02
 C026-C02C \\sim C3-C6
 with sigma of 0.02
 C028-C02A \\sim C4-C5
 with sigma of 0.02
 C028-C02C \\sim C4-C6
 with sigma of 0.02
 N018-C01W \\sim N0-C2
 with sigma of 0.04
 N018-C026 \\sim N0-C3
 with sigma of 0.04
 C01S-C01V \\sim C01S-C1
 with sigma of 0.04
 C01V-C022 \\sim C1-C0
 with sigma of 0.04
 C01V-C02A \\sim C1-C5
 with sigma of 0.04
 C01V-C02B \\sim C1-C7
 with sigma of 0.04
 C01V-C02C \\sim C1-C6
 with sigma of 0.04
 C01W-C026 \\sim C2-C3
 with sigma of 0.04
 C01W-C028 \\sim C2-C4
 with sigma of 0.04
 C022-C02A \\sim C0-C5
 with sigma of 0.04
 C026-C028 \\sim C3-C4
 with sigma of 0.04
 C02A-C02C \\sim C5-C6
 with sigma of 0.04
 C02B-C02C \\sim C7-C6
 with sigma of 0.04
 C021-C02D \\sim C8-C9
 with sigma of 0.02
 C021-C02F \\sim C8-C10
 with sigma of 0.02
 C02D-C02I \\sim C9-C12
 with sigma of 0.02
 C02D-C02J \\sim C9-C13
 with sigma of 0.02
 C02F-C02G \\sim C10-C14
 with sigma of 0.02
 C02F-C02K \\sim C10-C02L
 with sigma of 0.02
 C02H-C02J \\sim C11-C13
 with sigma of 0.02
 C02H-C02K \\sim C11-C02L
 with sigma of 0.02
 C00V-C021 \\sim C00V-C8
 with sigma of 0.04
 C021-C02G \\sim C8-C14
 with sigma of 0.04
 C021-C02I \\sim C8-C12
 with sigma of 0.04
 C021-C02J \\sim C8-C13
 with sigma of 0.04
 C021-C02K \\sim C8-C02L
 with sigma of 0.04
 C02D-C02F \\sim C9-C10
 with sigma of 0.04
 C02D-C02H \\sim C9-C11
 with sigma of 0.04
 C02F-C02H \\sim C10-C11
 with sigma of 0.04
 C02G-C02K \\sim C14-C02L
 with sigma of 0.04
 C02I-C02J \\sim C12-C13
 with sigma of 0.04
 C02J-C02K \\sim C13-C02L
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C021) \\sim Ueq, Uanis(C02D) \\sim Ueq, Uanis(C02F) \\sim Ueq,
Uanis(C02G) \\sim Ueq, Uanis(C02H) \\sim Ueq, Uanis(C02I) \\sim Ueq,
Uanis(C02J) \\sim Ueq, Uanis(C02K) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C02L) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(N00I)
\\sim Ueq, Uanis(N00J) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(N018) \\sim Ueq, Uanis(C01C) \\sim Ueq, Uanis(C01G) \\sim Ueq,
Uanis(C01L) \\sim Ueq, Uanis(C01S) \\sim Ueq, Uanis(C01T) \\sim Ueq,
Uanis(C01V) \\sim Ueq, Uanis(C01W) \\sim Ueq, Uanis(C020) \\sim Ueq,
Uanis(C022) \\sim Ueq, Uanis(C026) \\sim Ueq, Uanis(C028) \\sim Ueq,
Uanis(C029) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C02B) \\sim Ueq,
Uanis(C02C) \\sim Ueq, Uanis(N0) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C0) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C02E)
\\sim Ueq, Uanis(C01Y) \\sim Ueq, Uanis(C024) \\sim Ueq, Uanis(C01R) \\sim Ueq:
with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(N0)=Sof(C1)=Sof(C2)=Sof(C0)=Sof(H0A)=Sof(H0B)=Sof(H0C)=Sof(C3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=1-
 FVAR(1)
 Sof(N018)=Sof(C01V)=Sof(C01W)=Sof(C022)=Sof(H02Q)=Sof(H02R)=Sof(H02S)=
 Sof(C026)=Sof(C028)=Sof(H028)=Sof(C02A)=Sof(H02Z)=Sof(C02B)=Sof(H02)=Sof(H)=
 Sof(HA)=Sof(C02C)=Sof(H1)=FVAR(1)
 Sof(N00J)=Sof(H00J)=Sof(C8)=Sof(C9)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13)=Sof(C02L)=Sof(H02P)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(2)
 Sof(N00I)=Sof(C021)=Sof(C02D)=Sof(C02F)=Sof(C02G)=Sof(H02G)=Sof(H02H)=
 Sof(H02I)=Sof(C02H)=Sof(H02J)=Sof(C02I)=Sof(H02K)=Sof(H02L)=Sof(H02M)=
 Sof(C02J)=Sof(H02N)=Sof(C02K)=Sof(H02O)=Sof(H00I)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C00H(H00A,H00B)
5.b Aromatic/amide H refined with riding coordinates:
 C00M(H00M), C012(H012), C017(H017), C01E(H01E), C01K(H01K), C01M(H01M),
 C01O(H01O), C01Q(H01Q), C01U(H01U), C01X(H01X), C028(H028), C02A(H02Z),
 C02C(H1), C02H(H02J), C02J(H02N), C02K(H02O), C4(H4), C5(H5), C6(H6),
 N00J(H00J), C11(H11), C13(H13), C02L(H02P)
5.c Idealised Me refined as rotating group:
 C00T(H00C,H00D,H00E), C014(H01A,H01B,H01C), C01H(H01D,H01F,H01G), C01L(H01H,
 H01I,H01J), C01T(H01L,H01N,H01P), C01Z(H01R,H01S,H01T), C022(H02Q,H02R,H02S),
 C023(H02A,H02B,H02C), C024(H02T,H02U,H02V), C025(H02D,H02E,H02F), C029(H02W,
 H02X,H02Y), C02B(H02,H,HA), C02E(H2,HB,HC), C02G(H02G,H02H,H02I), C02I(H02K,
 H02L,H02M), C0(H0A,H0B,H0C), C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C14(H14A,
 H14B,H14C)
;
_shelx_res_checksum              16542
_shelx_fab_checksum              70869
_olex2_submission_special_instructions 'No special instructions were received'