Visible-light driven H<sub>2</sub> reductive elimination unlocks reactivity in polyhydrido niobium iridium clusters.
Dubrawski, Zachary; Aïssiou, Samy; Jeanneau, Erwann; Thieuleux, Chloé; Camp, Clément; Dalton transactions (Cambridge, England : 2003) 55 (2026) 620–629; doi:10.1039/d5dt02432c

data_7720504
_publ_section_title
;
 Visible-light driven H<sub>2</sub> reductive elimination unlocks
 reactivity in polyhydrido niobium iridium clusters.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              620
_journal_page_last               629
_journal_paper_doi               10.1039/d5dt02432c
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C48 H58 Ir3 Nb O, C5 H12'
_chemical_formula_sum            'C53 H70 Ir3 Nb O'
_chemical_formula_weight         1392.700
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-21
_audit_creation_method
;
Olex2 1.5-ac6-012
(compiled 2023.08.24 svn.re1ec1418 for Rigaku Oxford Diffraction, GUI svn.r6817)
;
_audit_update_record
;
2025-09-11 deposited with the CCDC.	2025-11-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.515(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3515(3)
_cell_length_b                   12.1117(2)
_cell_length_c                   26.2377(5)
_cell_measurement_reflns_used    35362
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      30.2580
_cell_measurement_theta_min      2.3960
_cell_volume                     4981.86(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.93a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.93a 64-bit (release 17-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-ac6-012 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.9993
_diffrn_measured_fraction_theta_max 0.8625
_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     -5.00  44.00   0.50   10.00    --    8.76 -97.00  36.00   98
  2  \w    -23.00  39.00   0.50   10.00    --   -7.66  57.00  60.00  124
  3  \w    -60.00   8.00   0.50   10.00    --   -7.66 -57.00 120.00  136
  4  \w    -60.00   8.00   0.50   10.00    --   -7.66 -57.00  60.00  136
  5  \w    -60.00   8.00   0.50   10.00    --   -7.66 -57.00  60.00  136
  6  \w    -60.00   8.00   0.50   10.00    --   -7.66 -57.00 120.00  136
  7  \w    -72.00 -40.00   0.50   10.00    --    8.76 -19.00   0.00   64
  8  \w    -72.00 -40.00   0.50   10.00    --    8.76 -19.00  30.00   64
  9  \w     -4.00  46.00   0.50   10.00    --    8.76 -99.00-120.00  100
 10  \w     -7.00  39.00   0.50   10.00    --    8.76  57.00 150.00   92
 11  \w    -72.00 -40.00   0.50   10.00    --    8.76 -19.00 -60.00   64
 12  \w     -7.00  30.00   0.50   10.00    --    8.76  38.00   0.00   74
 13  \w    -72.00 -40.00   0.50   10.00    --    8.76 -19.00-150.00   64
;
_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      0.0200193000
_diffrn_orient_matrix_UB_12      -0.0006291000
_diffrn_orient_matrix_UB_13      0.0277829000
_diffrn_orient_matrix_UB_21      -0.0135520000
_diffrn_orient_matrix_UB_22      0.0550370000
_diffrn_orient_matrix_UB_23      0.0019232000
_diffrn_orient_matrix_UB_31      -0.0382513000
_diffrn_orient_matrix_UB_32      -0.0199963000
_diffrn_orient_matrix_UB_33      0.0043868000
_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  0.0628
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.9993
_diffrn_reflns_Laue_measured_fraction_max 0.8625
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            89765
_diffrn_reflns_point_group_measured_fraction_full 0.9993
_diffrn_reflns_point_group_measured_fraction_max 0.8625
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         30.39
_diffrn_reflns_theta_min         2.33
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.247
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41346
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.93a (Rigaku Oxford Diffraction, 2023)
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    1.857
_exptl_crystal_description       block
_exptl_crystal_F_000             2672.0
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.156
_refine_diff_density_max         2.1016
_refine_diff_density_min         -2.1614
_refine_diff_density_rms         0.4215
_refine_ls_d_res_high            0.7025
_refine_ls_d_res_low             8.7243
_refine_ls_goodness_of_fit_ref   1.0287
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    143
_refine_ls_number_parameters     748
_refine_ls_number_reflns         12981
_refine_ls_number_restraints     1779
_refine_ls_restrained_S_all      0.9612
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0646
_refine_ls_shift/su_max          0.0009
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+184.5641P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1315
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              21
_reflns_limit_h_min              -22
_reflns_limit_k_max              16
_reflns_limit_k_min              0
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                11131
_reflns_number_total             12981
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5dt02432c2.cif
_cod_data_source_block           ZD018_autored
_cod_database_code               7720504
_chemical_oxdiff_formula         'C30 H30 N1 Nb1 Ir3 '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C42B-C41A = C42B-C43B = C41A-C40B = C40B-C39B = C39B-C43B
 1.42 with sigma of 0.02
 C42B-C47B = C43B-C48B
 1.5 with sigma of 0.02
 C41A-C46B = C40B-C45B = C39B-C44B
 1.51 with sigma of 0.02
 C42A-C41B = C42A-C43A = C41B-C40A = C40A-C39A = C39A-C43A
 1.42 with sigma of 0.02
 C42A-C47A = C43A-C48A
 1.5 with sigma of 0.02
 C41B-C46A = C40A-C45A = C39A-C44A
 1.51 with sigma of 0.02
 C33A-C29A = C33A-C32A = C29A-C30A = C30A-C31A = C31A-C32A
 1.42 with sigma of 0.02
 C33A-C38A = C32A-C37A
 1.5 with sigma of 0.02
 C29A-C34A = C30A-C35A = C31A-C36A
 1.51 with sigma of 0.02
 C29B-C30B = C29B-C33B = C30B-C31B = C31B-C32B = C32B-C33B
 1.42 with sigma of 0.02
 C29B-C34B = C33B-C38B
 1.5 with sigma of 0.02
 C30B-C35B = C31B-C36B = C32B-C37B
 1.51 with sigma of 0.02
 C42B-C40B = C42B-C39B
 2.29 with sigma of 0.04
 C42B-C46B = C42B-C48B = C41A-C45B
 2.6 with sigma of 0.04
 C41A-C39B = C40B-C43B
 2.3 with sigma of 0.04
 C40B-C44B = C39B-C48B
 2.61 with sigma of 0.04
 C42A-C40A = C42A-C39A
 2.29 with sigma of 0.04
 C42A-C46A = C42A-C48A = C41B-C45A
 2.6 with sigma of 0.04
 C41B-C39A = C40A-C43A
 2.3 with sigma of 0.04
 C40A-C44A = C39A-C48A
 2.61 with sigma of 0.04
 C33A-C30A = C33A-C31A
 2.29 with sigma of 0.04
 C33A-C34A = C33A-C37A = C29A-C35A
 2.6 with sigma of 0.04
 C29A-C31A = C30A-C32A
 2.3 with sigma of 0.04
 C30A-C36A = C31A-C37A
 2.61 with sigma of 0.04
 C29B-C31B = C29B-C32B
 2.29 with sigma of 0.04
 C29B-C35B = C29B-C38B = C30B-C36B
 2.6 with sigma of 0.04
 C30B-C32B = C31B-C33B
 2.3 with sigma of 0.04
 C31B-C37B = C32B-C38B
 2.61 with sigma of 0.04
 C33A-C29A \\sim C29A-C30A \\sim C30A-C31A \\sim C31A-C32A \\sim C32A-C33A
 with sigma of 0.02
 C33A-C30A \\sim C29A-C31A \\sim C30A-C32A \\sim C32A-C29A \\sim C33A-C31A
 with sigma of 0.04
 C33A-C38A \\sim C29A-C34A \\sim C30A-C35A \\sim C31A-C36A \\sim C32A-C37A
 with sigma of 0.02
 C38A-C29A \\sim C38A-C32A \\sim C34A-C33A \\sim C34A-C30A \\sim C35A-C29A
\\sim C35A-C31A \\sim C36A-
 C30A \\sim C36A-C32A \\sim C37A-C31A \\sim C37A-C33A
 with sigma of 0.04
 C29B-C30B \\sim C30B-C31B \\sim C31B-C32B \\sim C32B-C33B \\sim C33B-C29B
 with sigma of 0.02
 C29B-C31B \\sim C30B-C32B \\sim C31B-C33B \\sim C33B-C30B \\sim C29B-C32B
 with sigma of 0.04
 C29B-C34B \\sim C30B-C35B \\sim C31B-C36B \\sim C32B-C37B \\sim C33B-C38B
 with sigma of 0.02
 C34B-C30B \\sim C34B-C33B \\sim C35B-C29B \\sim C35B-C31B \\sim C36B-C30B
\\sim C36B-C32B \\sim C37B-
 C31B \\sim C37B-C33B \\sim C38B-C32B \\sim C38B-C29B
 with sigma of 0.04
3. Restrained planarity
 C45B, C48B, C42B, C47B, C41A, C44B, C40B, C46B, C39B, C43B
 with sigma of 0.1
 C44A, C43A, C46A, C42A, C48A, C41B, C45A, C40A, C47A, C39A
 with sigma of 0.1
 C33A, C29A, C30A, C31A, C32A, C37A, C36A, C35A, C34A, C38A
 with sigma of 0.1
 C29B, C30B, C31B, C32B, C33B, C38B, C37B, C36B, C35B, C34B
 with sigma of 0.1
 C30B, C31B, C32B, C33B, C29B, C34B, C38B, C37B, C36B, C35B
 with sigma of 0.1
 C35A, C30A, C29A, C34A, C33A, C38A, C32A, C37A, C31A, C36A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C40B \\sim C44B \\sim C45B \\sim C40A \\sim C44A \\sim C45A \\sim C42B \\sim
C41A \\sim C39B \\sim C43B \\sim C48B \\sim C46B \\sim C47B \\sim C42A \\sim
C41B \\sim C39A \\sim C43A \\sim C48A \\sim C46A \\sim C47A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C40B \\sim C39B \\sim C43B \\sim C48B \\sim C44B \\sim C45B \\sim C39A \\sim
C43A \\sim C48A \\sim C44A \\sim C45A \\sim C42B \\sim C47B \\sim C42A \\sim
C47A \\sim C41A \\sim C46B \\sim C41B \\sim C40A \\sim C46A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C33A \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C37A \\sim C36A \\sim
C35A \\sim C34A \\sim C38A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C35A \\sim C35B \\sim C29A \\sim C30A \\sim C31A \\sim C36A \\sim C34A \\sim
C29B \\sim C30B \\sim C31B \\sim C36B \\sim C34B \\sim C33A \\sim C32A \\sim
C37A \\sim C38A \\sim C32B \\sim C33B \\sim C38B \\sim C37B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C33A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C30A) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C37A) \\sim Ueq,
Uanis(C36A) \\sim Ueq, Uanis(C35A) \\sim Ueq, Uanis(C34A) \\sim Ueq,
Uanis(C38A) \\sim Ueq, Uanis(C29B) \\sim Ueq, Uanis(C30B) \\sim Ueq,
Uanis(C31B) \\sim Ueq, Uanis(C32B) \\sim Ueq, Uanis(C33B) \\sim Ueq,
Uanis(C38B) \\sim Ueq, Uanis(C37B) \\sim Ueq, Uanis(C36B) \\sim Ueq,
Uanis(C35B) \\sim Ueq, Uanis(C34B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C40B, C44B, C45B, C46B, C40A, C39A, C44A, C45A, C42B, C41A, C39B, C43B, C48B,
 C47B, C42A, C41B, C43A, C48A, C46A, C47A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41A, C46B, C47B, C42A, C41B, C47A, C46A, C40B, C43B, C48B, C40A, C39A, C43A,
 C48A, C39B, C44B, C45B, C44A, C45A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33A, C29A, C30A, C31A, C32A, C37A, C36A, C35A, C34A, C38A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29A, C30A, C31A, C36A, C34A, C29B, C30B, C31B, C36B, C34B, C33A, C32A, C37A,
 C38A, C32B, C33B, C38B, C37B, C35A, C35B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Ir2B(0.5) Ir3A(0.5) Ir3B(0.5) C42B(0.5) C41A(0.5) C40B(0.5)
 C39B(0.5) C43B(0.5) C48B(0.5) H48a(0.5) H48b(0.5) H48c(0.5) C44B(0.5)
 H44a(0.5) H44b(0.5) H44c(0.5) C45B(0.5) H45a(0.5) H45b(0.5) H45c(0.5)
 C46B(0.5) H46a(0.5) H46b(0.5) H46c(0.5) C47B(0.5) H47a(0.5) H47b(0.5)
 H47c(0.5) C42A(0.5) C41B(0.5) C40A(0.5) C39A(0.5) C43A(0.5) C48A(0.5)
 H48d(0.5) H48e(0.5) H48f(0.5) C44A(0.5) H44d(0.5) H44e(0.5) H44f(0.5)
 C45A(0.5) H45d(0.5) H45e(0.5) H45f(0.5) C46A(0.5) H46d(0.5) H46e(0.5)
 H46f(0.5) C47A(0.5) H47d(0.5) H47e(0.5) H47f(0.5) Ir2A(0.5) C33A(0.5)
 C29A(0.5) C30A(0.5) C31A(0.5) C32A(0.5) C37A(0.5) H37a(0.5) H37b(0.5)
 H37c(0.5) C36A(0.5) H36a(0.5) H36b(0.5) H36c(0.5) C35A(0.5) H35a(0.5)
 H35b(0.5) H35c(0.5) C34A(0.5) H34a(0.5) H34b(0.5) H34c(0.5) C38A(0.5)
 H38a(0.5) H38b(0.5) H38c(0.5) C29B(0.5) C30B(0.5) C31B(0.5) C32B(0.5)
 C33B(0.5) C38B(0.5) H38d(0.5) H38e(0.5) H38f(0.5) C37B(0.5) H37d(0.5)
 H37e(0.5) H37f(0.5) C36B(0.5) H36d(0.5) H36e(0.5) H36f(0.5) C35B(0.5)
 H35d(0.5) H35e(0.5) H35f(0.5) C34B(0.5) H34d(0.5) H34e(0.5) H34f(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C52(H52a,H52b), C51(H51a,H51b), C50(H50a,H50b)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C18(H18), C5(H5), C17(H17), C12(H12), C10(H10),
 C16(H16), C14(H14), C11(H11), C15(H15), C9(H9)
7.c Idealised Me refined as rotating group:
 C24(H24a,H24b,H24c), C25(H25a,H25b,H25c), C28(H28a,H28b,H28c), C26(H26a,H26b,
 H26c), C27(H27a,H27b,H27c), C53(H53a,H53b,H53c), C49(H49a,H49b,H49c),
 C48B(H48a,H48b,H48c), C44B(H44a,H44b,H44c), C45B(H45a,H45b,H45c), C46B(H46a,
 H46b,H46c), C47B(H47a,H47b,H47c), C48A(H48d,H48e,H48f), C44A(H44d,H44e,H44f),
 C45A(H45d,H45e,H45f), C46A(H46d,H46e,H46f), C47A(H47d,H47e,H47f), C37A(H37a,
 H37b,H37c), C36A(H36a,H36b,H36c), C35A(H35a,H35b,H35c), C34A(H34a,H34b,H34c),
 C38A(H38a,H38b,H38c), C38B(H38d,H38e,H38f), C37B(H37d,H37e,H37f), C36B(H36d,
 H36e,H36f), C35B(H35d,H35e,H35f), C34B(H34d,H34e,H34f)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id ZD018
_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 2.191
_oxdiff_exptl_absorpt_empirical_full_min 0.397