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_1575153
_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         'C16 H33 Ir Mo N3'
_chemical_formula_sum            'C16 H33 Ir Mo N3'
_chemical_formula_weight         555.59
_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             2024-01-15
_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                 90.251(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3443(4)
_cell_length_b                   8.22852(16)
_cell_length_c                   13.3820(3)
_cell_measurement_reflns_used    28376
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.1480
_cell_measurement_theta_min      2.6990
_cell_volume                     2019.95(7)
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.894
_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    -60.00   8.00   0.50    1.23    --   -7.80 -57.00 120.00  136
  2  \w    -60.00   8.00   0.50    1.23    --   -7.80 -57.00  60.00  136
  3  \w    -40.00  11.00   0.50    1.23    --   -7.80 -66.00-107.00  102
  4  \w    -89.00 -40.00   0.50    1.23    --   -7.80 -19.00-150.00   98
  5  \w    -89.00 -40.00   0.50    1.23    --   -7.80 -19.00 -30.00   98
  6  \w    -23.00  39.00   0.50    1.23    --   -7.80  57.00 -60.00  124
  7  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00  90.00   64
  8  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00 120.00   64
  9  \w     -7.00  18.00   0.50    1.23    --    8.74  57.00  60.00   50
 10  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00 150.00   64
 11  \w    -40.00  27.00   0.50    1.23    --    8.74 -66.00-107.00  134
 12  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00-120.00   64
 13  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00-150.00   64
 14  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00-180.00   64
 15  \w    -72.00 -40.00   0.50    1.23    --    8.74 -19.00  30.00   64
 16  \w     -4.00  46.00   0.50    1.23    --    8.74 -99.00 -30.00  100
 17  \w     -4.00  46.00   0.50    1.23    --    8.74 -99.00  60.00  100
 18  \w     -4.00  46.00   0.50    1.23    --    8.74 -99.00-180.00  100
;
_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      0.0236900000
_diffrn_orient_matrix_UB_12      -0.0502491000
_diffrn_orient_matrix_UB_13      0.0283612000
_diffrn_orient_matrix_UB_21      0.0305036000
_diffrn_orient_matrix_UB_22      0.0423488000
_diffrn_orient_matrix_UB_23      -0.0193466000
_diffrn_orient_matrix_UB_31      -0.0018021000
_diffrn_orient_matrix_UB_32      0.0557806000
_diffrn_orient_matrix_UB_33      0.0403901000
_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  0.0822
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.894
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            46772
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.334
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.201
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12572
_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    1.827
_exptl_crystal_description       plate
_exptl_crystal_F_000             1076
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.741
_refine_diff_density_min         -4.443
_refine_diff_density_rms         0.242
_refine_ls_extinction_coef       0.00067(14)
_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   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         5431
_refine_ls_number_restraints     919
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0495
_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^+17.8463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1114
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4428
_reflns_number_total             5431
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03465e2.cif
_cod_data_source_block           zd036_2
_cod_depositor_comments
'Adding full bibliography for 1575153--1575159.cif.'
_cod_original_cell_volume        2019.94(7)
_cod_database_code               1575153
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C56 H72 I8 N40 O8 Ir1 Mo1 '
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.187
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C11A-C10A = C11A-C7A = C10A-C9A = C9A-C8A = C8A-C7A
 1.42 with sigma of 0.02
 C11A-C16A = C7A-C12A
 1.5 with sigma of 0.02
 C10A-C15A = C9A-C14A = C8A-C13A
 1.51 with sigma of 0.02
 C11A-C9A = C11A-C8A
 2.29 with sigma of 0.04
 C11A-C15A = C11A-C12A = C10A-C14A
 2.6 with sigma of 0.04
 C10A-C8A = C9A-C7A
 2.3 with sigma of 0.04
 C9A-C13A = C8A-C12A
 2.61 with sigma of 0.04
 C11A-C10A \\sim C10A-C9A \\sim C9A-C8A \\sim C8A-C7A \\sim C7A-C11A
 with sigma of 0.02
 C11A-C9A \\sim C10A-C8A \\sim C9A-C7A \\sim C7A-C10A \\sim C11A-C8A
 with sigma of 0.04
 C11A-C16A \\sim C10A-C15A \\sim C9A-C14A \\sim C8A-C13A \\sim C7A-C12A
 with sigma of 0.02
 C16A-C10A \\sim C16A-C7A \\sim C15A-C11A \\sim C15A-C9A \\sim C14A-C10A \\sim
C14A-C8A \\sim C13A-C9A
 \\sim C13A-C7A \\sim C12A-C8A \\sim C12A-C11A
 with sigma of 0.04
 C11A-C10A \\sim C11B-C10B
 with sigma of 0.02
 C11A-C7A \\sim C11B-C7B
 with sigma of 0.02
 C11A-C16A \\sim C11B-C16B
 with sigma of 0.02
 C10A-C9A \\sim C10B-C9B
 with sigma of 0.02
 C10A-C15A \\sim C10B-C15B
 with sigma of 0.02
 C9A-C8A \\sim C9B-C8B
 with sigma of 0.02
 C9A-C14A \\sim C9B-C14B
 with sigma of 0.02
 C8A-C7A \\sim C8B-C7B
 with sigma of 0.02
 C8A-C13A \\sim C8B-C13B
 with sigma of 0.02
 C7A-C12A \\sim C7B-C12B
 with sigma of 0.02
 Ir1-C11A \\sim Ir1-C11B
 with sigma of 0.04
 Ir1-C10A \\sim Ir1-C10B
 with sigma of 0.04
 Ir1-C9A \\sim Ir1-C9B
 with sigma of 0.04
 Ir1-C8A \\sim Ir1-C8B
 with sigma of 0.04
 Ir1-C7A \\sim Ir1-C7B
 with sigma of 0.04
 Ir1-C12A \\sim Ir1-C12B
 with sigma of 0.04
 Ir1-C13A \\sim Ir1-C13B
 with sigma of 0.04
 Ir1-C14A \\sim Ir1-C14B
 with sigma of 0.04
 Ir1-C15A \\sim Ir1-C15B
 with sigma of 0.04
 Ir1-C16A \\sim Ir1-C16B
 with sigma of 0.04
 C11A-C9A \\sim C11B-C9B
 with sigma of 0.04
 C11A-C8A \\sim C11B-C8B
 with sigma of 0.04
 C11A-C12A \\sim C11B-C12B
 with sigma of 0.04
 C11A-C15A \\sim C11B-C15B
 with sigma of 0.04
 C10A-C8A \\sim C10B-C8B
 with sigma of 0.04
 C10A-C7A \\sim C10B-C7B
 with sigma of 0.04
 C10A-C14A \\sim C10B-C14B
 with sigma of 0.04
 C10A-C16A \\sim C10B-C16B
 with sigma of 0.04
 C9A-C7A \\sim C9B-C7B
 with sigma of 0.04
 C9A-C13A \\sim C9B-C13B
 with sigma of 0.04
 C9A-C15A \\sim C9B-C15B
 with sigma of 0.04
 C8A-C12A \\sim C8B-C12B
 with sigma of 0.04
 C8A-C14A \\sim C8B-C14B
 with sigma of 0.04
 C7A-C13A \\sim C7B-C13B
 with sigma of 0.04
 C7A-C16A \\sim C7B-C16B
 with sigma of 0.04
 C7B-C12B \\sim C16A-C11A \\sim C16B-C11B \\sim C15A-C10A \\sim C15B-C10B \\sim
C9A-C14A \\sim C9B-
 C14B \\sim C8A-C13A \\sim C8B-C13B \\sim C7A-C12A
 with sigma of 0.01
 C11A-C10A \\sim C11B-C10B \\sim C9A-C10A \\sim C9B-C10B \\sim C9A-C8A \\sim
C9B-C8B \\sim C8B-C7B ~
 C8A-C7A \\sim C7A-C11A \\sim C7B-C11B
 with sigma of 0.01
3. Restrained planarity
 C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A
\\sim C15A \\sim C16A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
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 \\sim C14A
\\sim C14B \\sim C15A \\sim C15B \\sim C16A \\sim C16B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7A, C7B, C8A, C8B, C9A, C9B, C10A, C10B, C11A, C11B, C12A, C12B, C13A, C13B,
 C14A, C14B, C15A, C15B, C16A, C16B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C7B)=Sof(C8B)=Sof(C9B)=Sof(C10B)=Sof(C11B)=Sof(C12B)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16B)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(C7A)=Sof(C8A)=Sof(C9A)=Sof(C10A)=Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
7.a Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F),
 C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F), C14A(H14A,H14B,H14C), C14B(H14D,
 H14E,H14F), C15A(H15A,H15B,H15C), C15B(H15D,H15E,H15F), C16A(H16A,H16B,H16C),
 C16B(H16D,H16E,H16F)
;
_shelx_res_checksum              50285
_olex2_submission_original_sample_id ZD036
_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 4.427
_oxdiff_exptl_absorpt_empirical_full_min 0.627