Synergistic C-H bond activation across molybdenum-iridium multiply bonded complexes: a cascade of transformations.
Dubrawski, Zachary; Del Rosal, Iker; Jeanneau, Erwann; Maron, Laurent; Thieuleux, Chloé; Camp, Clément; Chemical science 16 (2025) 14564–14577; doi:10.1039/d5sc03465e

data_1575158
_publ_section_title
;
 Synergistic C-H bond activation across molybdenum-iridium multiply bonded
 complexes: a cascade of transformations.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              14564
_journal_page_last               14577
_journal_paper_doi               10.1039/d5sc03465e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C26 H42 Ir2 Mo N2 O4'
_chemical_formula_sum            'C26 H42 Ir2 Mo N2 O4'
_chemical_formula_weight         926.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-12
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2024-12-16 deposited with the CCDC.	2025-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.354(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.9967(2)
_cell_length_b                   10.9728(2)
_cell_length_c                   12.1515(2)
_cell_measurement_reflns_used    21076
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      30.0530
_cell_measurement_theta_min      2.4900
_cell_volume                     1466.23(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-015 (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      150.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.888
_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  32.00   0.50    0.70    --    8.73 -77.00-180.00  106
  2  \w    -72.00 -40.00   0.50    0.70    --    8.73 -19.00 -90.00   64
  3  \w    -72.00 -40.00   0.50    0.70    --    8.73 -19.00  30.00   64
  4  \w    -72.00 -40.00   0.50    0.70    --    8.73 -19.00   0.00   64
  5  \w    -72.00 -40.00   0.50    0.70    --    8.73 -19.00 -60.00   64
  6  \w    -72.00 -46.00   0.50    0.70    --    8.73 -19.00 120.00   52
  7  \w     -7.00  39.00   0.50    0.70    --    8.73  57.00  90.00   92
  8  \w     -7.00  39.00   0.50    0.70    --    8.73  57.00  30.00   92
  9  \w    -72.00 -40.00   0.50    0.70    --    8.73 -19.00-120.00   64
 10  \w    -88.00  -7.00   0.50    0.70    --   -7.72 -35.00-158.00  162
 11  \w    -88.00  -7.00   0.50    0.70    --   -7.72 -35.00-158.00  162
 12  \w     -4.00  46.00   0.50    0.70    --    8.73 -99.00 -60.00  100
 13  \w     -4.00  46.00   0.50    0.70    --    8.73 -99.00  90.00  100
 14  \w    -24.00  74.00   0.50    0.70    --   -7.72  35.00  -1.00  196
 15  \w    -24.00  74.00   0.50    0.70    --   -7.72  35.00  -1.00  196
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0626351000
_diffrn_orient_matrix_UB_12      0.0050006000
_diffrn_orient_matrix_UB_13      -0.0135265000
_diffrn_orient_matrix_UB_21      0.0109517000
_diffrn_orient_matrix_UB_22      -0.0286330000
_diffrn_orient_matrix_UB_23      -0.0513399000
_diffrn_orient_matrix_UB_31      -0.0108296000
_diffrn_orient_matrix_UB_32      -0.0577496000
_diffrn_orient_matrix_UB_33      0.0242405000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0461
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.888
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            33776
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.888
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.307
_diffrn_reflns_theta_min         2.490
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.507
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.100
_exptl_crystal_description       plate
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.068
_refine_diff_density_max         2.020
_refine_diff_density_min         -2.134
_refine_diff_density_rms         0.164
_refine_ls_extinction_coef       0.00019(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3901
_refine_ls_number_restraints     623
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0352
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0108P)^2^+11.4969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0638
_refine_ls_wR_factor_ref         0.0668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3310
_reflns_number_total             3901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03465e2.cif
_cod_data_source_block           zd067_autored
_cod_depositor_comments
'Adding full bibliography for 1575153--1575159.cif.'
_cod_database_code               1575158
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H84 Ir4 Mo2 N4 O8 '
_shelx_estimated_absorpt_t_max   0.564
_shelx_estimated_absorpt_t_min   0.186
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4B-C5B \\sim C4A-C5A
 with sigma of 0.02
 C4B-C8B \\sim C4A-C8A
 with sigma of 0.02
 C4B-C9B \\sim C4A-C9A
 with sigma of 0.02
 C5B-C6B \\sim C5A-C6A
 with sigma of 0.02
 C5B-C10B \\sim C5A-C10A
 with sigma of 0.02
 C8B-C7B \\sim C8A-C7A
 with sigma of 0.02
 C8B-C13B \\sim C8A-C13A
 with sigma of 0.02
 C6B-C7B \\sim C6A-C7A
 with sigma of 0.02
 C6B-C11B \\sim C6A-C11A
 with sigma of 0.02
 C7B-C12B \\sim C7A-C12A
 with sigma of 0.02
 Ir1-C4B \\sim Ir1-C4A
 with sigma of 0.04
 Ir1-C5B \\sim Ir1-C5A
 with sigma of 0.04
 Ir1-C8B \\sim Ir1-C8A
 with sigma of 0.04
 Ir1-C6B \\sim Ir1-C6A
 with sigma of 0.04
 Ir1-C7B \\sim Ir1-C7A
 with sigma of 0.04
 Ir1-C9B \\sim Ir1-C9A
 with sigma of 0.04
 Ir1-C10B \\sim Ir1-C10A
 with sigma of 0.04
 Ir1-C11B \\sim Ir1-C11A
 with sigma of 0.04
 Ir1-C12B \\sim Ir1-C12A
 with sigma of 0.04
 Ir1-C13B \\sim Ir1-C13A
 with sigma of 0.04
 C4B-C6B \\sim C4A-C6A
 with sigma of 0.04
 C4B-C7B \\sim C4A-C7A
 with sigma of 0.04
 C4B-C10B \\sim C4A-C10A
 with sigma of 0.04
 C4B-C13B \\sim C4A-C13A
 with sigma of 0.04
 C5B-C8B \\sim C5A-C8A
 with sigma of 0.04
 C5B-C7B \\sim C5A-C7A
 with sigma of 0.04
 C5B-C9B \\sim C5A-C9A
 with sigma of 0.04
 C5B-C11B \\sim C5A-C11A
 with sigma of 0.04
 C8B-C6B \\sim C8A-C6A
 with sigma of 0.04
 C8B-C9B \\sim C8A-C9A
 with sigma of 0.04
 C8B-C12B \\sim C8A-C12A
 with sigma of 0.04
 C6B-C10B \\sim C6A-C10A
 with sigma of 0.04
 C6B-C12B \\sim C6A-C12A
 with sigma of 0.04
 C7B-C11B \\sim C7A-C11A
 with sigma of 0.04
 C7B-C13B \\sim C7A-C13A
 with sigma of 0.04
 C9B-C4B \\sim C9A-C4A \\sim C10B-C5B \\sim C10A-C5A \\sim C11B-C6B \\sim
C11A-C6A \\sim C12B-C7B ~
 C12A-C7A \\sim C13B-C8B \\sim C13A-C8A
 with sigma of 0.01
 C6B-C5B \\sim C6A-C5A \\sim C6A-C7A \\sim C7B-C6B \\sim C7B-C8B \\sim C8A-C7A
\\sim C8B-C4B \\sim C8A-C4A
 \\sim C4A-C5A \\sim C5B-C4B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C4A \\sim C4B \\sim C5A \\sim C5B \\sim C6A \\sim C6B \\sim C7A \\sim C7B \\sim
C8A \\sim C8B \\sim C9A \\sim C9B \\sim C10A \\sim C10B \\sim C11A \\sim C11B
\\sim C12A \\sim C12B \\sim C13A \\sim C13B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C4A, C4B, C5A, C5B, C6A, C6B, C7A, C7B, C8A, C8B, C9A, C9B, C10A, C10B, C11A,
 C11B, C12A, C12B, C13A, C13B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11A)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=
 Sof(H13A)=Sof(H13B)=Sof(H13C)=1-FVAR(1)
 Sof(C4B)=Sof(C5B)=Sof(C6B)=Sof(C7B)=Sof(C8B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=
 Sof(H9BC)=Sof(C10B)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11B)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13B)=
 Sof(H13D)=Sof(H13E)=Sof(H13F)=FVAR(1)
6.a Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C9A(H9AA,H9AB,H9AC), C9B(H9BA,H9BB,H9BC),
 C10A(H10A,H10B,H10C), C10B(H10D,H10E,H10F), C11A(H11A,H11B,H11C), C11B(H11D,
 H11E,H11F), C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F), C13A(H13A,H13B,H13C),
 C13B(H13D,H13E,H13F)
;
_shelx_res_checksum              59429
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id ZD067
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.612
_oxdiff_exptl_absorpt_empirical_full_min 0.766