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_1573566
_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         'C60 H81 B3 N6 O'
_chemical_formula_sum            'C60 H81 B3 N6 O'
_chemical_formula_weight         934.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/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                 99.0810(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.24980(10)
_cell_length_b                   13.50310(10)
_cell_length_c                   37.4373(2)
_cell_measurement_reflns_used    33208
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2020
_cell_measurement_theta_min      2.3910
_cell_volume                     11106.73(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_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 0.980
_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     21.00  46.00   0.50    0.76    --   56.98-107.00 -40.00   50
  2  \w     49.00  75.00   0.50    0.76    --   69.64-107.00 -40.00   52
  3  \w     72.00 106.00   0.50    0.76    --   84.06-107.00 -40.00   68
  4  \w      4.00  36.00   0.50    0.76    --   56.98 -30.00  30.00   64
  5  \w      9.00  34.00   0.50    0.76    --   56.98 -30.00-120.00   50
  6  \w      5.00  34.00   0.50    0.76    --   56.98 -30.00   0.00   58
  7  \w      5.00  32.00   0.50    0.76    --   56.98 -30.00 -60.00   54
  8  \w     65.00  91.00   0.50    0.76    --   56.98  45.00-120.00   52
  9  \w     20.00  45.00   0.50    0.76    --   69.64 -45.00  60.00   50
 10  \w     19.00  44.00   0.50    0.76    --   69.64 -45.00 120.00   50
 11  \w     26.00  75.00   0.50    0.76    --   69.64 -94.00-150.00   98
 12  \w     69.00 111.00   0.50    0.76    --   69.64  77.00-120.00   84
 13  \w     46.00  97.00   0.50    0.76    --   69.64-125.00  60.00  102
 14  \w     40.00  69.00   0.50    0.76    --   69.64 -94.00  60.00   58
 15  \w    104.00 134.00   0.50    0.76    --   84.06  30.00-180.00   60
 16  \w     96.00 122.00   0.50    0.76    --   84.06  45.00 -90.00   52
 17  \w     40.00  79.00   0.50    0.76    --   84.06 -94.00  30.00   78
 18  \w     89.00 134.00   0.50    0.76    --   84.06  45.00-150.00   90
 19  \w     52.00  78.00   0.50    0.76    --   84.06-111.00  30.00   52
 20  \w     37.00  63.00   0.50    0.76    --   84.06 -61.00  60.00   52
 21  \w     57.00  84.00   0.50    0.76    --   84.06 -77.00  60.00   54
 22  \w     43.00  77.00   0.50    0.76    --   84.06 -94.00   0.00   68
 23  \w     43.00  84.00   0.50    0.76    --   84.06 -77.00  30.00   82
 24  \w     89.00 116.00   0.50    0.76    --   84.06  30.00  60.00   54
 25  \w     81.00 107.00   0.50    0.76    --   84.06  30.00 -90.00   52
 26  \w     44.00  86.00   0.50    0.76    --   84.06 -77.00-150.00   84
 27  \w     82.00 107.00   0.50    0.76    --   84.06-111.00  30.00   50
 28  \w     38.00  63.00   0.50    0.76    --   84.06 -61.00  30.00   50
 29  \w     89.00 114.00   0.50    0.76    --   84.06  45.00 -60.00   50
 30  \w     59.00 110.00   0.50    0.76    --   86.75  23.00 176.52  102
 31  \w     90.00 122.00   0.50    0.76    --   86.75  11.00 -43.71   64
 32  \w     57.00  82.00   0.50    0.76    --   86.75  11.00 -43.71   50
 33  \w     59.00  94.00   0.50    0.76    --   86.75  17.00 124.28   70
 34  \w     42.00  78.00   0.50    0.76    --   86.75 -64.00-111.66   72
 35  \w     74.00 132.00   0.50    0.76    --   86.75  24.00  27.00  116
 36  \w     45.00 100.00   0.50    0.76    --   86.75 -98.00 -97.62  110
 37  \w    -22.00   3.00   0.50    0.76    --   -6.75  98.00 156.00   50
 38  \w     53.00 110.00   0.50    0.76    --   56.98  30.00 150.00  114
 39  \w      5.00  35.00   0.50    0.76    --   56.98 -30.00 -90.00   60
 40  \w      5.00  31.00   0.50    0.76    --   56.98 -30.00 -30.00   52
 41  \w     66.00 110.00   0.50    0.76    --   69.64  77.00 -30.00   88
 42  \w     29.00  74.00   0.50    0.76    --   69.64 -94.00 -90.00   90
 43  \w     84.00 114.00   0.50    0.76    --   69.64  61.00-150.00   60
 44  \w     22.00  48.00   0.50    0.76    --   69.64-125.00-180.00   52
 45  \w     77.00 103.00   0.50    0.76    --   69.64-125.00 -30.00   52
 46  \w     34.00  59.00   0.50    0.76    --   69.64 -94.00 120.00   50
 47  \w     89.00  97.00   0.50    0.76    --   69.64  30.00  30.00   16
;
_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      0.0141838000
_diffrn_orient_matrix_UB_12      -0.1097159000
_diffrn_orient_matrix_UB_13      0.0089514000
_diffrn_orient_matrix_UB_21      0.0148895000
_diffrn_orient_matrix_UB_22      -0.0161887000
_diffrn_orient_matrix_UB_23      -0.0383800000
_diffrn_orient_matrix_UB_31      0.0670310000
_diffrn_orient_matrix_UB_32      0.0269140000
_diffrn_orient_matrix_UB_33      0.0135198000
_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  0.0205
_diffrn_reflns_av_unetI/netI     0.0133
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            67625
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.836
_diffrn_reflns_theta_min         2.390
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.498
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92218
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.95a (Rigaku Oxford Diffraction, 2023)
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    1.118
_exptl_crystal_description       block
_exptl_crystal_F_000             4048
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         11344
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0501P)^2^+6.6257P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1037
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9976
_reflns_number_total             11344
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07487d2.cif
_cod_data_source_block           435jtaec23_auto
_cod_depositor_comments
'Adding full bibliography for 1573562--1573567.cif.'
_cod_database_code               1573566
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H20'
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.961
_olex2_refinement_description
;
1. Restrained distances
 C25-C26A \\sim C25-C26B
 with sigma of 0.02
 C25-C27A \\sim C25-C27B
 with sigma of 0.02
 C32-C34A \\sim C32-C34B
 with sigma of 0.02
 C32-C33B \\sim C32-C33A
 with sigma of 0.02
 C20-C22A \\sim C20-C22B
 with sigma of 0.02
 C20-C21A \\sim C20-C21B
 with sigma of 0.02
2. Rigid bond restraints
 C27B, C25, C26B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27B, C25
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C33A, C32, C34B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21B, C20, C22B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C26B, C25
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C27B: within 2A with sigma of 0.05 and sigma for terminal atoms of 0.05 within
2A
C22B: within 2A with sigma of 0.05 and sigma for terminal atoms of 0.1 within 2A
Uanis(C27B) \\sim Ueq: with sigma of 0.012 and sigma for terminal atoms of 0.02
Uanis(C22B) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
Uanis(C26B) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
Uanis(C27A) = Uanis(C27B)
Uanis(C26A) = Uanis(C26B)
4. Rigid body (RIGU) restrains
 C25, C27B, C26B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34B, C32, C33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C21B, C22B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H25A)=Sof(C27B)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C26B)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(H25)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=Sof(H27A)=
 Sof(H27B)=Sof(H27C)=FVAR(1)
 Sof(H32A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34B)=Sof(H34D)=
 Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(H32)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C33B)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=FVAR(2)
 Sof(H20A)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=1-FVAR(3)
 Sof(H20)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C21A)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C59(H59), C52(H52), C40(H40), C20(H20), C20(H20A), C47(H47), C13(H13),
 C32(H32), C32(H32A), C25(H25), C25(H25A)
6.b Aromatic/amide H refined with riding coordinates:
 N4(H4), N1(H1), C36(H36), C37(H37), C9(H9), C10(H10), C57(H57), C55(H55),
 C45(H45), C56(H56), C18(H18), C43(H43), C17(H17), C16(H16), C8(H8), C44(H44),
 C30(H30), C28(H28), C4(H4A), C7(H7), C29(H29), C6(H6), C5(H5)
6.c X=CH2 refined with riding coordinates:
 C2(H2A,H2B)
6.d Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C54(H54A,H54B,H54C), C53(H53A,H53B,H53C), C61(H61A,H61B,
 H61C), C48(H48A,H48B,H48C), C15(H15A,H15B,H15C), C49(H49A,H49B,H49C), C42(H42A,
 H42B,H42C), C41(H41A,H41B,H41C), C14(H14A,H14B,H14C), C22A(H22A,H22B,H22C),
 C34A(H34A,H34B,H34C), C26A(H26A,H26B,H26C), C33B(H33A,H33B,H33C), C21A(H21A,
 H21B,H21C), C27A(H27A,H27B,H27C), C27B(H27D,H27E,H27F), C26B(H26D,H26E,H26F),
 C33A(H33D,H33E,H33F), C34B(H34D,H34E,H34F), C21B(H21D,H21E,H21F), C22B(H22D,
 H22E,H22F)
;
_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 1.249
_oxdiff_exptl_absorpt_empirical_full_min 0.762