Synthesis of symmetrical and unsymmetrical cyclic diborenes via NHC-directed C–H borylation
Mihm, Cornelius; Kar, Sourav; Sachs, Andreas; Duwe, Dario; Dewhurst, Rian D.; Braunschweig, Holger; Chemical Science 16 (2025) 11637–11643; doi:10.1039/D5SC03150H

data_1574725
_publ_section_title
;
 Synthesis of symmetrical and unsymmetrical cyclic diborenes via
 NHC-directed C--H borylation
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              11637
_journal_page_last               11643
_journal_paper_doi               10.1039/D5SC03150H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C44 H54 B2 N4, C22 H28 B I N2'
_chemical_formula_sum            'C66 H82 B3 I N6'
_chemical_formula_weight         1118.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-04-28
_audit_creation_method           'CIF-fill 1.6d (K.Radacki, 2005-25)'
_audit_update_record
;
2025-04-29 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.274(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6024(3)
_cell_length_b                   21.2733(2)
_cell_length_c                   21.6009(3)
_cell_measurement_reflns_used    32292
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.2340
_cell_measurement_theta_min      2.8390
_cell_volume                     7157.95(18)
_computing_cell_refinement       'CrysAlisPro 1.171.43.89a (Rigaku OD, 2023)'
_computing_data_collection
;
 CrysAlisPro system (CCD 42.102a 64-bit (release 15-09-2023))
;
_computing_data_reduction        'CrysAlisPro 1.171.43.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
 
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w     99.00 124.00   0.50    0.34    --   85.25  55.00   6.38   50
  2  \w     99.00 133.00   0.50    0.34    --   85.25  54.00  52.22   68
  3  \w    109.00 134.00   0.50    0.34    --   85.25  45.00  31.87   50
  4  \w     97.00 135.00   0.50    0.34    --   85.25  32.00 -14.43   76
  5  \w     59.00  93.00   0.50    0.34    --   46.00  52.00  19.61   68
  6  \w     62.00  90.00   0.50    0.34    --   46.00  52.00 -28.41   56
  7  \w     78.00 125.00   0.50    0.34    --   85.25  21.00-167.79   94
  8  \w    100.00 134.00   0.50    0.34    --   85.25  42.00-106.22   68
  9  \w    105.00 136.00   0.50    0.34    --   85.25  30.00 -80.75   62
 10  \w     71.00  99.00   0.50    0.34    --   82.26  15.00 -90.00   56
 11  \w     63.00 134.00   0.50    0.34    --   85.25  13.00   5.18  142
 12  \w     93.00 127.00   0.50    0.34    --   82.26  15.00  90.00   68
 13  \w     98.00 133.00   0.50    0.34    --   85.25  16.00 150.32   70
 14  \w     63.00  92.00   0.50    0.34    --   85.25  16.00 150.32   58
 15  \w     47.00  72.00   0.50    0.34    --   82.26  15.00  90.00   50
 16  \w    104.00 134.00   0.50    0.34    --   85.25  12.00-138.29   60
 17  \w     48.00  83.00   0.50    0.34    --   85.25 -83.00 -77.14   70
 18  \w     39.00  76.00   0.50    0.34    --   85.25-137.00 -89.23   74
 19  \w     62.00  88.00   0.50    0.34    --   85.25-140.00 -25.93   52
 20  \w     42.00 103.00   0.50    0.34    --   85.25-132.00-158.88  122
 21  \w     40.00 102.00   0.50    0.34    --   85.25-129.00 -42.18  124
 22  \w     39.00  68.00   0.50    0.34    --   85.25-126.00  66.22   58
 23  \w     69.00 106.00   0.50    0.34    --   85.25-136.00 105.72   74
 24  \w     68.00 101.00   0.50    0.34    --   85.25-126.00 161.06   66
 25  \w     39.00  66.00   0.50    0.34    --   85.25-126.00 161.06   54
 26  \w     39.00  90.00   0.50    0.34    --   85.25-139.00 158.85  102
 27  \w     44.00  69.00   0.50    0.34    --   82.26-123.00  94.00   50
 28  \w     37.00  94.00   0.50    0.34    --   71.26-123.00  94.00  114
 29  \w     18.00  84.00   0.50    0.34    --   58.45-123.00  94.00  132
 30  \w     48.00  89.00   0.50    0.34    --   85.25-113.00 109.23   82
 31  \w     43.00  97.00   0.50    0.34    --   85.25-119.00  22.70  108
 32  \w     37.00  62.00   0.50    0.34    --   82.26-112.00 120.00   50
 33  \w     42.00  68.00   0.50    0.34    --   82.26-112.00  90.00   52
 34  \w     42.00  74.00   0.50    0.34    --   85.25-109.00  57.91   64
 35  \w     39.00  80.00   0.50    0.34    --   85.25-125.00 -72.55   82
 36  \w     43.00  90.00   0.50    0.34    --   85.25-108.00 -28.65   94
 37  \w     67.00 101.00   0.50    0.34    --   85.25-126.00 -78.56   68
 38  \w     48.00  93.00   0.50    0.34    --   85.25-101.00 -23.11   90
 39  \w     64.00  91.00   0.50    0.34    --   85.25-111.00 -82.43   54
 40  \w     40.00  65.00   0.50    0.34    --   85.25-105.00-159.26   50
 41  \w     47.00  93.00   0.50    0.34    --   85.25-101.00-170.94   92
 42  \w     43.00  92.00   0.50    0.34    --   85.25 -95.00-142.37   98
 43  \w     50.00  92.00   0.50    0.34    --   85.25 -96.00  23.60   84
 44  \w     63.00  90.00   0.50    0.34    --   82.26 -95.00  60.00   54
 45  \w     64.00  90.00   0.50    0.34    --   82.26 -95.00  90.00   52
 46  \w     40.00  65.00   0.50    0.34    --   82.26 -95.00 150.00   50
 47  \w     92.00 126.00   0.50    0.34    --   85.25 137.00 -53.48   68
 48  \w     48.00  74.00   0.50    0.34    --   85.25 -87.00-170.16   52
 49  \w   -106.00 -42.00   0.50    0.34    --  -79.50 136.00-137.36  128
 50  \w    -96.00 -53.00   0.50    0.34    --  -79.50 115.00 -45.09   86
 51  \w    -97.00 -33.00   0.50    0.34    --  -79.50 116.00 124.82  128
 52  \w    -69.00 -26.00   0.50    0.34    --  -60.36 123.00 174.00   86
 53  \w    -83.00 -58.00   0.50    0.34    --  -69.85 123.00 174.00   50
 54  \w    -89.00 -64.00   0.50    0.34    --  -76.37 123.00 174.00   50
 55  \w    -97.00 -59.00   0.50    0.34    --  -78.00 114.00 118.59   76
 56  \w    -97.00 -72.00   0.50    0.34    --  -78.00 114.00 -84.01   50
 57  \w   -123.00 -98.00   0.50    0.34    --  -79.50 -66.00  43.95   50
 58  \w   -115.00 -90.00   0.50    0.34    --  -70.00 -55.00 142.62   50
 59  \w   -119.00 -92.00   0.50    0.34    --  -79.50 -62.00 -30.31   54
 60  \w   -115.00 -85.00   0.50    0.34    --  -70.00 -57.00-166.66   60
 61  \w   -126.00 -92.00   0.50    0.34    --  -79.50 -57.00-107.93   68
 62  \w    -98.00 -72.00   0.50    0.34    --  -58.00 -50.00 -56.89   52
 63  \w   -124.00 -99.00   0.50    0.34    --  -79.50 -65.00 -47.00   50
 64  \w    -93.00 -65.00   0.50    0.34    --  -46.00 -51.00  59.09   56
 65  \w   -103.00 -68.00   0.50    0.34    --  -54.00 -50.00  88.02   70
 66  \w   -122.00 -93.00   0.50    0.34    --  -79.50 -50.00  75.59   58
 67  \w   -125.00 -93.00   0.50    0.34    --  -79.50 -48.00 175.24   64
 68  \w   -125.00 -94.00   0.50    0.34    --  -79.50-119.00 138.40   62
 69  \w   -126.00-101.00   0.50    0.34    --  -79.50-120.00-103.96   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
;
 CrysAlisPro convention (1999,Acta A55,543-557)
;
_diffrn_orient_matrix_UB_11      -0.0669239000
_diffrn_orient_matrix_UB_12      0.0001330000
_diffrn_orient_matrix_UB_13      0.0497098000
_diffrn_orient_matrix_UB_21      -0.0720984000
_diffrn_orient_matrix_UB_22      -0.0098612000
_diffrn_orient_matrix_UB_23      -0.0508209000
_diffrn_orient_matrix_UB_31      0.0097351000
_diffrn_orient_matrix_UB_32      -0.0717759000
_diffrn_orient_matrix_UB_33      0.0070606000
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0750
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            146852
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.644
_diffrn_reflns_theta_min         2.837
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet-R X-ray Source'
_exptl_absorpt_coefficient_mu    3.792
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.870
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.43.89a (Rigaku Oxford Diffraction, 2023) 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            red
_exptl_crystal_density_diffrn    1.038
_exptl_crystal_description       block
_exptl_crystal_F_000             2352
_exptl_crystal_preparation
;
 For data collection the crystal was immersed in a film of perfluoropolyether 
 oil, mounted on a polyimide loop and transferred to stream of cold nitrogen 
 (Oxford Cryostream 800).
;
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.060
_refine_diff_density_max         1.081
_refine_diff_density_min         -1.246
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1085
_refine_ls_number_reflns         14662
_refine_ls_number_restraints     3150
_refine_ls_restrained_S_all      0.951
_refine_ls_R_factor_all          0.0907
_refine_ls_R_factor_gt           0.0707
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1226P)^2^+5.6207P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1936
_refine_ls_wR_factor_ref         0.2109
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10936
_reflns_number_total             14662
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03150h2.cif
_cod_data_source_block           diborene_3
_cod_depositor_comments
'Adding full bibliography for 1574720--1574725.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1574725
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.659
_shelx_estimated_absorpt_t_max   0.804
_shelx_res_checksum              8861
_shelx_fab_checksum              65765