Cascade Reductive Friedel‒Crafts Alkylation Catalyzed by Robust Iridium(III) Hydride Complexes Containing a Protic Triazolylidene Ligand
Alshakova, Iryna D.; Albrecht, Martin; ACS Catalysis  (2021) 8999–9007; doi:10.1021/acscatal.1c00740

data_4518874
_publ_section_title
;
 Cascade Reductive Friedel--Crafts Alkylation Catalyzed by Robust
 Iridium(III) Hydride Complexes Containing a Protic Triazolylidene Ligand
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              8999
_journal_page_last               9007
_journal_paper_doi               10.1021/acscatal.1c00740
_journal_year                    2021
_chemical_formula_moiety         'C23 H23 Br Cl Ir N4'
_chemical_formula_sum            'C23 H23 Br Cl Ir N4'
_chemical_formula_weight         663.01
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.7080(3)
_cell_length_b                   9.78149(14)
_cell_length_c                   24.7192(4)
_cell_measurement_reflns_used    5584
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.5150
_cell_measurement_theta_min      1.9700
_cell_volume                     4523.42(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.62a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.62a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.62a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0965
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.929
_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    -15.00  83.00   1.00   22.50    --   27.55 -99.00 -90.00   98
  2  \w    -48.00  65.00   1.00   22.50    --   27.55 -57.00-180.00  113
  3  \w    -16.00  42.00   1.00   22.50    --   27.55  77.00-150.00   58
  4  \w    -16.00  30.00   1.00   22.50    --   27.55  77.00   0.00   46
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0051568000
_diffrn_orient_matrix_UB_12      0.0190002000
_diffrn_orient_matrix_UB_13      0.0274109000
_diffrn_orient_matrix_UB_21      0.0364095000
_diffrn_orient_matrix_UB_22      0.0146905000
_diffrn_orient_matrix_UB_23      -0.0055185000
_diffrn_orient_matrix_UB_31      -0.0092471000
_diffrn_orient_matrix_UB_32      0.0684224000
_diffrn_orient_matrix_UB_33      -0.0064334000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            20341
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.125
_diffrn_reflns_theta_min         1.975
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.806
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71355
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.62a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.947
_exptl_crystal_description       plate
_exptl_crystal_F_000             2544
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.025
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         5125
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0143P)^2^+4.7482P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0550
_refine_ls_wR_factor_ref         0.0626
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3655
_reflns_number_total             5125
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00740_si_003.cif
_cod_data_source_block           19MA135_Ir017
_cod_original_cell_volume        4523.41(12)
_cod_database_code               4518874
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C168 H168 Br8 Cl8 Ir8 N48 '
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.509
_diffrn_oxdiff_digest_frames
;
01cd6fa32e1e189c40be72869df99509ee0030000ed
;
_diffrn_oxdiff_digest_hkl
;
011ff04c51aea0d00a61d48ef52ca23360b82b
;
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C23(H23), C27(H27), C26(H26), C24(H24), C14(H14), C13(H13), C15(H15), C12(H12)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C),
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              37339
_shelx_hkl_checksum              99076
_olex2_date_sample_data_collection 2019-12-02
_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 1.332
_oxdiff_exptl_absorpt_empirical_full_min 0.771