Catalytic H/D exchange of (hetero)arenes with early-late polyhydride heterobimetallic complexes: impact of transition metal pairs.
Lachguar, Abdelhak; Neumann, Till; Pichugov, Andrey V.; Jeanneau, Erwann; Veyre, Laurent; Thieuleux, Chloé; Camp, Clément; Dalton transactions (Cambridge, England : 2003) 54 (2025) 3804–3811; doi:10.1039/d4dt03171g

data_7717851
_publ_section_title
;
 Catalytic H/D exchange of (hetero)arenes with early-late polyhydride
 heterobimetallic complexes: impact of transition metal pairs.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3804
_journal_page_last               3811
_journal_paper_doi               10.1039/d4dt03171g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C25 H48 Hf Os'
_chemical_formula_sum            'C25 H48 Hf Os'
_chemical_formula_weight         717.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-15
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2024-11-04 deposited with the CCDC.	2025-01-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.428(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0703(2)
_cell_length_b                   11.9968(2)
_cell_length_c                   18.9180(4)
_cell_measurement_reflns_used    24681
_cell_measurement_temperature    100.1(2)
_cell_measurement_theta_max      30.5610
_cell_measurement_theta_min      2.3660
_cell_volume                     2797.47(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.120a 64-bit (release 16-04-2024))'
_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      100.1(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 0.993
_diffrn_measured_fraction_theta_max 0.844
_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     -6.00  39.00   0.50    2.14    --    7.11  57.00 120.00   90
  2  \w    -85.00 -40.00   0.50    2.14    --   -6.25 -19.00 -60.00   90
  3  \w    -85.00 -40.00   0.50    2.14    --   -6.25 -19.00 -30.00   90
  4  \w     25.00  86.00   0.50    2.14    --    7.11  13.00 -92.00  122
  5  \w     25.00  72.00   0.50    2.14    --   -6.25  13.00 -92.00   94
  6  \w     -6.00  32.00   0.50    2.14    --    7.11  57.00 -30.00   76
  7  \w    -73.00 -40.00   0.50    2.14    --    7.11 -19.00   0.00   66
  8  \w    -73.00 -40.00   0.50    2.14    --    7.11 -19.00-120.00   66
  9  \w     -4.00  42.00   0.50    2.14    --    7.11 -99.00 120.00   92
;
_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      0.0517303000
_diffrn_orient_matrix_UB_12      0.0101840000
_diffrn_orient_matrix_UB_13      0.0269733000
_diffrn_orient_matrix_UB_21      0.0234733000
_diffrn_orient_matrix_UB_22      0.0004445000
_diffrn_orient_matrix_UB_23      -0.0288411000
_diffrn_orient_matrix_UB_31      -0.0092198000
_diffrn_orient_matrix_UB_32      0.0582412000
_diffrn_orient_matrix_UB_33      -0.0045150000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.844
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            34091
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.420
_diffrn_reflns_theta_min         2.369
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16873
_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            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.703
_exptl_crystal_description       plate
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.443
_exptl_crystal_size_mid          0.328
_exptl_crystal_size_min          0.085
_refine_diff_density_max         2.228
_refine_diff_density_min         -2.610
_refine_diff_density_rms         0.225
_refine_ls_extinction_coef       0.00053(7)
_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   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         7148
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0284
_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^)+(0.0563P)^2^+0.2244P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0787
_refine_ls_wR_factor_ref         0.0808
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6451
_reflns_number_total             7148
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03171g2.cif
_cod_data_source_block           al159_autored
_cod_depositor_comments          'Adding full bibliography for 7717851.cif.'
_cod_database_code               7717851
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C100 H192 Os4 Ta4 '
_shelx_estimated_absorpt_t_max   0.541
_shelx_estimated_absorpt_t_min   0.121
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C11(H11A,H11B), C21(H21A,H21B)
2.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C18(H18A,H18B,
 H18C), C25(H25A,H25B,H25C), C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C9(H9A,H9B,
 H9C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C24(H24A,H24B,H24C), C10(H10A,H10B,
 H10C), C13(H13A,H13B,H13C), C6(H6A,H6B,H6C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id AL159
_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 2.477
_oxdiff_exptl_absorpt_empirical_full_min 0.572