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_1573564
_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         'C33 H40.398 B2 K N3 O2, 2[C6H6]'
_chemical_formula_sum            'C45 H52.4 B2 K N3 O2'
_chemical_formula_weight         728.01
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   mixed
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.7178(7)
_cell_length_b                   22.7178(7)
_cell_length_c                   15.9414(8)
_cell_measurement_reflns_used    6417
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.1570
_cell_measurement_theta_min      2.7350
_cell_volume                     8227.3(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.983
_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     17.00  48.00   0.50    0.50    --   56.98 -79.00  42.00   62
  2  \w     10.00  36.00   0.50    0.50    --   56.98 -42.00-139.00   52
  3  \w     30.00  55.00   0.50    0.50    --   56.98-123.00 157.00   50
  4  \w     70.00 105.00   0.50    0.50    --   56.98  42.00  12.00   70
  5  \w     49.00  75.00   0.50    0.50    --   69.64-123.00 157.00   52
  6  \w     34.00  60.00   0.50    0.50    --   69.64-149.00  -5.00   52
  7  \w     60.00  85.00   0.50    2.00    --   84.06-149.00  -5.00   50
  8  \w     49.00  74.00   0.50    2.00    --   84.06-123.00 157.00   50
  9  \w     94.00 123.00   0.50    2.00    --   84.06 123.00-121.00   58
 10  \w     95.00 120.00   0.50    2.00    --   84.06  42.00  12.00   50
 11  \w     71.00 109.00   0.50    0.50    --   69.64  77.00  60.00   76
 12  \w     20.00  53.00   0.50    0.50    --   69.64 -45.00  90.00   66
 13  \w     47.00  73.00   0.50    2.00    --   84.06 -61.00   0.00   52
 14  \w     40.00  66.00   0.50    2.00    --   84.06 -61.00-120.00   52
 15  \w     42.00  73.00   0.50    2.00    --   84.06 -61.00 120.00   62
 16  \w     48.00  87.00   0.50    2.00    --   84.06 -77.00-180.00   78
 17  \w     99.00 137.00   0.50    2.00    --   86.75  14.00 -44.79   76
 18  \w     57.00  82.00   0.50    2.00    --   86.75  14.00 -44.79   50
 19  \w     46.00  97.00   0.50    2.00    --   86.75   6.00-130.36  102
 20  \w    102.00 137.00   0.50    2.00    --   86.75  11.00  64.50   70
 21  \w     50.00  93.00   0.50    2.00    --   86.75  11.00  64.50   86
 22  \w     65.00 137.00   0.50    2.00    --   86.75  25.00-152.13  144
 23  \w     18.00  43.00   0.50    0.50    --   69.64 -42.00-139.00   50
 24  \w      6.00  32.00   0.50    0.50    --   56.98 -30.00 150.00   52
 25  \w     11.00  37.00   0.50    0.50    --   56.98 -30.00  60.00   52
 26  \w      9.00  35.00   0.50    0.50    --   56.98 -30.00 -30.00   52
 27  \w      4.00  29.00   0.50    0.50    --   56.98 -30.00 -90.00   50
 28  \w     35.00  81.00   0.50    0.50    --   69.64 -94.00-180.00   92
 29  \w     87.00 114.00   0.50    0.50    --   69.64  45.00  30.00   54
 30  \w     28.00  53.00   0.50    0.50    --   69.64 -45.00 -90.00   50
 31  \w     54.00  74.00   0.50    0.50    --   69.64 -94.00 -90.00   40
;
_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      0.0643607000
_diffrn_orient_matrix_UB_12      -0.0159171000
_diffrn_orient_matrix_UB_13      0.0208146000
_diffrn_orient_matrix_UB_21      0.0208777000
_diffrn_orient_matrix_UB_22      0.0319651000
_diffrn_orient_matrix_UB_23      -0.0799031000
_diffrn_orient_matrix_UB_31      0.0065204000
_diffrn_orient_matrix_UB_32      0.0574629000
_diffrn_orient_matrix_UB_33      0.0502039000
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30711
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.991
_diffrn_reflns_theta_min         2.751
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.428
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79972
_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    1.175
_exptl_crystal_description       block
_exptl_crystal_F_000             3107
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.248
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.040(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         8001
_refine_ls_number_restraints     283
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0551
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1280P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1600
_reflns_Friedel_coverage         0.824
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.875
_reflns_number_gt                7095
_reflns_number_total             8001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07487d2.cif
_cod_data_source_block           427jtaec23_1
_cod_depositor_comments
'Adding full bibliography for 1573562--1573567.cif.'
_cod_original_cell_volume        8227.3(7)
_cod_original_formula_sum        'C45 H52.40 B2 K N3 O2'
_cod_database_code               1573564
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 B2 N2'
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.882
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.96034
 0.03966
2. Restrained distances
 C8-C20A \\sim C8-C20B
 with sigma of 0.04
 N3A-C22A \\sim N3B-C22B
 with sigma of 0.02
 N3A-B2 \\sim N3B-B2
 with sigma of 0.02
 N3A-C21A \\sim N3B-C21B
 with sigma of 0.02
 C22A-C23A \\sim C22B-C23B
 with sigma of 0.02
 C22A-C30A \\sim C22B-C30B
 with sigma of 0.02
 C27A-C23A \\sim C27B-C23B
 with sigma of 0.02
 C27A-C28A \\sim C27B-C28B
 with sigma of 0.02
 C20A-C21A \\sim C20B-C21B
 with sigma of 0.02
 C28A-C29A \\sim C28B-C29B
 with sigma of 0.02
 C30A-C29A \\sim C30B-C29B
 with sigma of 0.02
 N3A-C23A \\sim N3B-C23B
 with sigma of 0.04
 N3A-C20A \\sim N3B-C20B
 with sigma of 0.04
 N3A-C30A \\sim N3B-C30B
 with sigma of 0.04
 C22A-C27A \\sim C22B-C27B
 with sigma of 0.04
 C22A-B2 \\sim C22B-B2
 with sigma of 0.04
 C22A-C21A \\sim C22B-C21B
 with sigma of 0.04
 C22A-C29A \\sim C22B-C29B
 with sigma of 0.04
 C27A-C29A \\sim C27B-C29B
 with sigma of 0.04
 B2-C20A \\sim B2-C20B
 with sigma of 0.04
 B2-C21A \\sim B2-C21B
 with sigma of 0.04
 C23A-C28A \\sim C23B-C28B
 with sigma of 0.04
 C23A-C30A \\sim C23B-C30B
 with sigma of 0.04
 C28A-C30A \\sim C28B-C30B
 with sigma of 0.04
 C33A-C31A \\sim C32B-C31B
 with sigma of 0.02
 C30B-C31A \\sim C30B-C31B
 with sigma of 0.02
 C31A-C32A \\sim C31B-C33B
 with sigma of 0.02
 C33A-C30B \\sim C32B-C30B
 with sigma of 0.04
 C33A-C32A \\sim C32B-C33B
 with sigma of 0.04
 C30B-C32A \\sim C30B-C33B
 with sigma of 0.04
 C17-C19B \\sim C17-C19A
 with sigma of 0.02
3. Rigid bond restraints
 C8, C9, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C27A)
\\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C23B) \\sim Ueq,
Uanis(C22B) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C30A) \\sim Ueq,
Uanis(C30B) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C31B) \\sim Ueq,
Uanis(C32B) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C32A) \\sim Ueq,
Uanis(C33B) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C29B) \\sim Ueq,
Uanis(C28A) \\sim Ueq, Uanis(C28B) \\sim Ueq, Uanis(N3A) \\sim Ueq, Uanis(N3B)
\\sim Ueq, Uanis(C21B) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C20B) \\sim Ueq,
Uanis(C20A) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
Uanis(C18B) \\sim Ueq, Uanis(C18A) \\sim Ueq: with sigma of 0.015 and sigma for
terminal atoms of 0.03
Uanis(C12B) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
5. Rigid body (RIGU) restrains
 C9, C8, C16, C15, C14, C13
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C18B, C17, C19B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18A, C17, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C24, C26
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=
 Sof(C22B)=Sof(C23B)=Sof(N3B)=Sof(C21B)=Sof(H21B)=Sof(C20B)=Sof(H20B)=1-FVAR(1)
 Sof(N3A)=Sof(C22A)=Sof(C27A)=Sof(H27A)=Sof(C23A)=Sof(C20A)=Sof(H20A)=
 Sof(C28A)=Sof(H28A)=Sof(C21A)=Sof(H21A)=Sof(C30A)=Sof(C29A)=Sof(H29A)=FVAR(1)
 Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C31B)=Sof(H31B)=Sof(C32B)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(2)
 Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(2)
 Sof(H17)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C18A)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=1-FVAR(3)
 Sof(H17A)=Sof(C19B)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C18B)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=FVAR(3)
 Sof(H10)=Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(4)
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C17(H17A), C17(H17), C10(H10), C31A(H31A), C31B(H31B)
7.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C7(H7), C14(H14), C15(H15), C27A(H27A), C6(H6), C20A(H20A),
 C28A(H28A), C3(H3), C21A(H21A), C5(H5), C29A(H29A), C4(H4), C27B(H27B),
 C28B(H28B), C29B(H29B), C21B(H21B), C20B(H20B)
7.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C19B(H19A,H19B,H19C), C33A(H33A,H33B,H33C), C12B(H12A,
 H12B,H12C), C32A(H32A,H32B,H32C), C33B(H33D,H33E,H33F), C32B(H32D,H32E,H32F),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C18B(H18A,H18B,H18C), C19A(H19D,H19E,
 H19F), C18A(H18D,H18E,H18F), C12A(H12D,H12E,H12F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.363
_oxdiff_exptl_absorpt_empirical_full_min 0.749