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_7720500
_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         1392.60
_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             2025-05-28
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-09-11 deposited with the CCDC.	2025-11-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.6860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.62790(10)
_cell_length_b                   14.23730(10)
_cell_length_c                   19.74350(10)
_cell_measurement_reflns_used    72265
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      78.5030
_cell_measurement_theta_min      2.8860
_cell_volume                     5065.13(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.111a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.111a 64-bit (release 13-05-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.111a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (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      100.02(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 0.999
_diffrn_measured_fraction_theta_max 0.962
_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     24.00  91.00   0.50    0.25    --   49.03-114.00 -79.00  134
  2  \w    -71.00  -2.00   0.50    0.25    --  -50.53 114.00  11.00  138
  3  \w    -71.00  -2.00   0.50    0.25    --  -50.53 114.00  11.00  138
  4  \w   -156.00 -93.00   0.50    1.02    --  -81.95-114.00 -79.00  126
  5  \w    -71.00  -8.00   0.50    1.02    --  -81.95 114.00  11.00  126
  6  \w     26.00  97.00   0.50    1.02    --   99.76-114.00 -79.00  142
  7  \w    115.00 174.00   0.50    1.02    --   99.76 114.00  11.00  118
  8  \w     37.00  97.00   0.50    1.02    --  111.05-114.00 -79.00  120
  9  \w    -23.00   3.00   0.50    0.25    --   14.00 105.00 146.22   52
 10  \w    -25.00   1.00   0.50    0.25    --   14.00 109.00 127.77   52
 11  \w     -5.00  22.00   0.50    0.25    --   18.00  81.00  53.41   54
 12  \w    -19.00  28.00   0.50    0.25    --  -50.53  38.00 -30.00   94
 13  \w   -126.00 -79.00   0.50    0.25    --  -50.53 -57.00 -90.00   94
 14  \w   -126.00 -79.00   0.50    0.25    --  -50.53 -57.00-150.00   94
 15  \w    -51.00  -8.00   0.50    1.02    --  -81.95  61.00 -60.00   86
 16  \w    -51.00  -8.00   0.50    1.02    --  -81.95  61.00-150.00   86
 17  \w    -51.00  -8.00   0.50    1.02    --  -81.95  61.00-180.00   86
 18  \w    -51.00  -8.00   0.50    1.02    --  -81.95  61.00 120.00   86
 19  \w   -167.00 -83.00   0.50    1.02    --  -90.25 -47.00  60.05  168
 20  \w     29.00  92.00   0.50    1.02    --   99.76 -95.00 -60.00  126
 21  \w     87.00 136.00   0.50    1.02    --   99.76  15.00  30.00   98
 22  \w    121.00 169.00   0.50    1.02    --   99.76  77.00 120.00   96
 23  \w     93.00 166.00   0.50    1.02    --   99.76  30.00 120.00  146
 24  \w     87.00 136.00   0.50    1.02    --   99.76  15.00 -90.00   98
 25  \w     42.00  75.00   0.50    1.02    --  111.05 -77.00   0.00   66
 26  \w     40.00  92.00   0.50    1.02    --  111.05 -95.00 -90.00  104
 27  \w     98.00 136.00   0.50    1.02    --  111.05  15.00 -30.00   76
 28  \w     98.00 136.00   0.50    1.02    --  111.05  15.00 -60.00   76
 29  \w     40.00  92.00   0.50    1.02    --  111.05 -95.00 -30.00  104
 30  \w     42.00  75.00   0.50    1.02    --  111.05 -77.00 -30.00   66
 31  \w     98.00 136.00   0.50    1.02    --  111.05  15.00   0.00   76
 32  \w    115.00 178.00   0.50    1.02    --  111.05 114.00  11.00  126
 33  \w     26.00  54.00   0.50    0.25    --   42.00  65.00 -30.13   56
 34  \w     32.00  58.00   0.50    0.25    --   46.00  62.00-154.87   52
 35  \w     32.00  58.00   0.50    0.25    --   46.00  61.00 100.01   52
 36  \w     32.00  58.00   0.50    0.25    --   46.00  62.00 -92.02   52
 37  \w     33.00  59.00   0.50    0.25    --   46.00  60.00  58.08   52
 38  \w     32.00  58.00   0.50    0.25    --   46.00  62.00 135.12   52
 39  \w   -150.00 -63.00   0.50    0.25    --  -74.00 -55.00 -68.52  174
 40  \w   -150.00 -64.00   0.50    0.25    --  -74.00 -52.00 170.54  172
 41  \w   -150.00 -64.00   0.50    0.25    --  -74.00 -52.00 -20.69  172
 42  \w   -150.00 -63.00   0.50    0.25    --  -74.00 -55.00 120.64  174
 43  \w   -150.00 -64.00   0.50    0.25    --  -74.00 -52.00  77.22  172
 44  \w   -154.00 -67.00   0.50    1.02    --  -78.00 -55.00-116.79  174
 45  \w   -162.00 -75.00   0.50    1.02    --  -86.00 -54.00  31.99  174
 46  \w   -165.00 -79.00   0.50    1.02    --  -90.25 -57.00-140.39  172
 47  \w   -165.00-103.00   0.50    1.02    --  -90.25 -59.00 118.92  124
 48  \w     87.00 136.00   0.50    1.02    --   99.76  15.00-150.00   98
 49  \w     31.00 100.00   0.50    1.02    --   99.76-125.00-150.00  138
 50  \w     29.00  92.00   0.50    1.02    --   99.76 -95.00  60.00  126
 51  \w     42.00  75.00   0.50    1.02    --  111.05 -77.00  60.00   66
 52  \w     42.00  75.00   0.50    1.02    --  111.05 -77.00 120.00   66
;
_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      0.0295893000
_diffrn_orient_matrix_UB_12      -0.0062280000
_diffrn_orient_matrix_UB_13      -0.0660132000
_diffrn_orient_matrix_UB_21      0.0786176000
_diffrn_orient_matrix_UB_22      0.0239975000
_diffrn_orient_matrix_UB_23      0.0442496000
_diffrn_orient_matrix_UB_31      0.0160870000
_diffrn_orient_matrix_UB_32      -0.1052558000
_diffrn_orient_matrix_UB_33      0.0139468000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            97566
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.852
_diffrn_reflns_theta_min         3.873
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    16.948
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.15081
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.111a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.826
_exptl_crystal_description       plate
_exptl_crystal_F_000             2672
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.438
_refine_diff_density_min         -1.420
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     540
_refine_ls_number_reflns         10505
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0255
_refine_ls_R_factor_gt           0.0250
_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^)+(0.0429P)^2^+11.2820P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0690
_refine_ls_wR_factor_ref         0.0694
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10302
_reflns_number_total             10505
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02432c2.cif
_cod_data_source_block           zd468_autored
_cod_database_code               7720500
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C53 H70 Ir3 Nb1 O1'
_shelx_estimated_absorpt_t_max   0.630
_shelx_estimated_absorpt_t_min   0.172
_diffrn_oxdiff_digest_od_ed
;

;
_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.a Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              63856
_shelx_hkl_checksum              84803
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id ZD468
_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 3.517
_oxdiff_exptl_absorpt_empirical_full_min 0.623