Metathesis chemistry of inorganic cumulenes driven by B-O bond formation.
Tang, Jianqin; Hu, Chenyang; Crumpton, Agamemnon E.; Griffin, Liam P.; Goicoechea, Jose M.; Aldridge, Simon; Chemical science 16 (2025) 2231–2237; doi:10.1039/d4sc07487d

data_1573562
_publ_section_title
;
 Metathesis chemistry of inorganic cumulenes driven by B-O bond formation.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              2231
_journal_page_last               2237
_journal_paper_doi               10.1039/d4sc07487d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C27 H36 B N3 O'
_chemical_formula_sum            'C27 H36 B N3 O'
_chemical_formula_weight         429.40
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-21
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-08-15 deposited with the CCDC.	2024-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.7556(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.67284(7)
_cell_length_b                   9.17962(5)
_cell_length_c                   22.43254(13)
_cell_measurement_reflns_used    39192
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.5180
_cell_measurement_theta_min      2.0140
_cell_volume                     2591.50(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     10.00  36.00   0.50    0.07    --   56.89 -30.00 -90.00   52
  2  \w      7.00  34.00   0.50    0.07    --   56.89 -30.00-120.00   54
  3  \w      4.00  33.00   0.50    0.07    --   56.89 -30.00 -30.00   58
  4  \w     10.00  36.00   0.50    0.07    --   56.89 -30.00  30.00   52
  5  \w     19.00  44.00   0.50    0.07    --   69.68 -45.00   0.00   50
  6  \w     80.00 116.00   0.50    0.07    --   69.68  61.00  90.00   72
  7  \w     20.00  46.00   0.50    0.07    --   69.68 -45.00 -60.00   52
  8  \w     22.00  47.00   0.50    0.07    --   69.68 -45.00-150.00   50
  9  \w     19.00  44.00   0.50    0.07    --   69.68 -45.00 150.00   50
 10  \w     21.00  53.00   0.50    0.07    --   69.68 -45.00  90.00   64
 11  \w     85.00 118.00   0.50    0.07    --   69.68  45.00 -60.00   66
 12  \w     79.00 112.00   0.50    0.07    --   69.68  61.00 150.00   66
 13  \w     21.00  47.00   0.50    0.07    --   69.68 -45.00  60.00   52
 14  \w     73.00 122.00   0.50    0.07    --   69.68  30.00  30.00   98
 15  \w     47.00  73.00   0.50    0.07    --   84.12  15.00 150.00   52
 16  \w     39.00  64.00   0.50    0.07    --   84.12 -61.00 120.00   50
 17  \w     83.00 111.00   0.50    0.07    --   84.12  30.00 -60.00   56
 18  \w    107.00 133.00   0.50    0.07    --   84.12  45.00-150.00   52
 19  \w     37.00  62.00   0.50    0.07    --   84.12 -61.00  30.00   50
 20  \w     37.00  62.00   0.50    0.07    --   84.12 -61.00   0.00   50
 21  \w     97.00 127.00   0.50    0.07    --   84.12   0.00-180.00   60
 22  \w     80.00 130.00   0.50    0.07    --   84.12  30.00-150.00  100
 23  \w     93.00 119.00   0.50    0.07    --   84.12  45.00 120.00   52
 24  \w     59.00  93.00   0.50    0.07    --   84.12   0.00-180.00   68
 25  \w     49.00  74.00   0.50    0.07    --   84.12 -77.00-180.00   50
 26  \w    108.00 137.00   0.50    0.07    --   84.12  30.00 -90.00   58
 27  \w    100.00 125.00   0.50    0.07    --   84.12  45.00-120.00   50
 28  \w     72.00  98.00   0.50    0.07    --   84.12-111.00 -90.00   52
 29  \w    104.00 134.00   0.50    0.07    --   84.12  15.00  60.00   60
 30  \w    103.00 129.00   0.50    0.07    --   84.12  15.00 150.00   52
 31  \w     38.00  63.00   0.50    0.07    --   84.12 -61.00-180.00   50
 32  \w     52.00 108.00   0.50    0.07    --   84.12-111.00 -60.00  112
 33  \w     38.00  70.00   0.50    0.07    --   84.12 -61.00  60.00   64
 34  \w     57.00  90.00   0.50    0.07    --   84.12 -95.00  30.00   66
 35  \w     44.00  70.00   0.50    0.07    --   84.12 -77.00 120.00   52
 36  \w     37.00  62.00   0.50    0.07    --   84.12 -61.00 150.00   50
 37  \w     87.00 125.00   0.50    0.07    --   84.12 178.00-150.00   76
 38  \w     53.00  81.00   0.50    0.07    --   84.12  15.00  60.00   56
 39  \w     46.00  71.00   0.50    0.07    --   84.12 -61.00-150.00   50
 40  \w     85.00 113.00   0.50    0.07    --   84.12  30.00-180.00   56
 41  \w     63.00  88.00   0.50    0.07    --   84.12 -77.00 -90.00   50
 42  \w     41.00  83.00   0.50    0.07    --   69.68-102.00 -50.00   84
 43  \w      7.00  50.00   0.50    0.07    --   56.89 -45.00 150.00   86
 44  \w     24.00  50.00   0.50    0.07    --   56.89-125.00 150.00   52
 45  \w     63.00  90.00   0.50    0.07    --   56.89-125.00 150.00   54
 46  \w     66.00  91.00   0.50    0.07    --   69.68  77.00  60.00   50
 47  \w     34.00 103.00   0.50    0.07    --   69.68-125.00-120.00  138
 48  \w     55.00  84.00   0.50    0.07    --   69.68 -95.00 150.00   58
 49  \w     36.00  61.00   0.50    0.07    --   69.68-125.00 -90.00   50
 50  \w     77.00 103.00   0.50    0.07    --   69.68-125.00 -90.00   52
 51  \w     76.00 117.00   0.50    0.07    --   69.68  45.00-120.00   82
 52  \w     39.00  85.00   0.50    0.07    --   69.68 -95.00  30.00   92
 53  \w     82.00 108.00   0.50    0.07    --   84.12-111.00  60.00   52
 54  \w     38.00  70.00   0.50    0.07    --   84.12-111.00  60.00   64
 55  \w     45.00  71.00   0.50    0.07    --   84.12 -77.00 -60.00   52
 56  \w     81.00 114.00   0.50    0.07    --   84.12  30.00-120.00   66
 57  \w     48.00 108.00   0.50    0.07    --   84.12-111.00   0.00  120
 58  \w     43.00  95.00   0.50    0.07    --   84.12 -95.00  60.00  104
 59  \w     40.00  65.00   0.50    0.07    --   84.12-111.00 150.00   50
 60  \w     44.00  70.00   0.50    0.07    --   84.12 -77.00-150.00   52
 61  \w     95.00 121.00   0.50    0.07    --   84.12  15.00 -90.00   52
 62  \w     74.00 108.00   0.50    0.07    --   84.12-111.00 120.00   68
 63  \w    103.00 132.00   0.50    0.07    --   84.12  15.00  90.00   58
 64  \w     75.00 106.00   0.50    0.07    --   84.12-111.00-120.00   62
 65  \w     53.00  86.00   0.50    0.07    --   84.12   0.00 -90.00   66
 66  \w     57.00 129.00   0.50    0.07    --   84.12 178.00  90.00  144
 67  \w     48.00  74.00   0.50    0.07    --   84.12  15.00-180.00   52
 68  \w     99.00 134.00   0.50    0.07    --   84.12  15.00-180.00   70
 69  \w     41.00  67.00   0.50    0.07    --   84.12 -95.00-180.00   52
 70  \w     93.00 135.00   0.50    0.07    --   84.12  45.00 -30.00   84
 71  \w     38.00  65.00   0.50    0.07    --   84.12 -61.00 -30.00   54
 72  \w     73.00 107.00   0.50    0.07    --   84.12-111.00  30.00   68
 73  \w     83.00 117.00   0.50    0.07    --   84.12  30.00 -30.00   68
 74  \w     53.00  78.00   0.50    0.07    --   84.12 -77.00 120.00   50
 75  \w     43.00  68.00   0.50    0.07    --   84.12 -77.00 -90.00   50
 76  \w     89.00 114.00   0.50    0.07    --   84.12  45.00  90.00   50
 77  \w     53.00  79.00   0.50    0.07    --   84.12 -95.00-150.00   52
 78  \w     72.00 103.00   0.50    0.07    --   84.12-111.00-150.00   62
 79  \w     46.00  73.00   0.50    0.07    --   84.12-111.00 -90.00   54
 80  \w     83.00 108.00   0.50    0.07    --   84.12-111.00 -90.00   50
 81  \w     81.00 106.00   0.50    0.07    --   84.12-111.00  90.00   50
 82  \w     47.00  73.00   0.50    0.07    --   84.12-111.00  90.00   52
 83  \w     74.00 108.00   0.50    0.07    --   84.12-111.00-180.00   68
 84  \w     44.00  69.00   0.50    0.07    --   84.12 -61.00 -90.00   50
 85  \w     79.00 107.00   0.50    0.07    --   84.12-111.00 150.00   56
 86  \w     46.00  76.00   0.50    0.07    --   86.75 -86.00 -95.32   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0368387000
_diffrn_orient_matrix_UB_12      0.0374388000
_diffrn_orient_matrix_UB_13      -0.0661124000
_diffrn_orient_matrix_UB_21      -0.0901039000
_diffrn_orient_matrix_UB_22      -0.1129081000
_diffrn_orient_matrix_UB_23      -0.0007014000
_diffrn_orient_matrix_UB_31      -0.0742283000
_diffrn_orient_matrix_UB_32      0.1184430000
_diffrn_orient_matrix_UB_33      0.0202224000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_av_unetI/netI     0.0099
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            56620
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.557
_diffrn_reflns_theta_min         3.512
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.512
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86229
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         5317
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0491P)^2^+0.9941P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1021
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5015
_reflns_number_total             5317
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07487d2.cif
_cod_data_source_block           363jtaec23
_cod_depositor_comments
'Adding full bibliography for 1573562--1573567.cif.'
_cod_database_code               1573562
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28 H35 N3 O2 B2'
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.951
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C25(H25), C13(H13), C18(H18), C6(H6)
1.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C11(H11), C21(H21), C23(H23), C9(H9), C22(H22), C10(H10)
1.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C), C26(H26A,H26B,
 H26C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C19(H19A,H19B,
 H19C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.276
_oxdiff_exptl_absorpt_empirical_full_min 0.844