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_4518872
_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         '4(C23 H25 Ir N4), C8 O2'
_chemical_formula_sum            'C100 H100 Ir4 N16 O2'
_chemical_formula_weight         2326.75
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.976(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   11.47440(10)
_cell_length_b                   17.1601(2)
_cell_length_c                   12.5381(2)
_cell_measurement_reflns_used    11892
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.7770
_cell_measurement_theta_min      2.1230
_cell_volume                     2255.76(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (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)'
_computing_structure_solution    'ShelXT (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 0.915
_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     35.00 122.00   1.00    6.50    --   27.84 178.00 150.00   87
  2  \w    -20.00  83.00   1.00    6.50    --   27.84 -99.00 150.00  103
  3  \w    -56.00 115.00   1.00    6.50    --   27.84  19.00 -30.00  171
  4  \w    -20.00  30.00   1.00    6.50    --  -25.00 -99.00 120.00   50
  5  \w    -63.00  -2.00   1.00    6.50    --  -25.00  57.00 -30.00   61
  6  \w    -10.00 104.00   1.00    6.50    --   27.84  57.00  90.00  114
;
_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      -0.0504552000
_diffrn_orient_matrix_UB_12      -0.0269543000
_diffrn_orient_matrix_UB_13      -0.0265116000
_diffrn_orient_matrix_UB_21      0.0244489000
_diffrn_orient_matrix_UB_22      -0.0092276000
_diffrn_orient_matrix_UB_23      -0.0421094000
_diffrn_orient_matrix_UB_31      0.0378662000
_diffrn_orient_matrix_UB_32      -0.0299455000
_diffrn_orient_matrix_UB_33      0.0368559000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.915
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            19328
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.145
_diffrn_reflns_theta_min         1.942
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.940
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88255
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (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    1.713
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.922
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         5060
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0254
_refine_ls_R_factor_gt           0.0208
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0175P)^2^+1.7304P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0468
_refine_ls_wR_factor_ref         0.0493
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4523
_reflns_number_total             5060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00740_si_004.cif
_cod_data_source_block           19MA114_IrH-1
_cod_database_code               4518872
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C23 H25 Ir1 N4'
_reflns_odcompleteness_completeness 99.98
_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. Uiso/Uaniso restraints and constraints
Uanis(C31) = Uanis(C31) = Uanis(C29) = Uanis(C29)
Uanis(C29) = Uanis(C31) = Uanis(C32)
Uanis(C29) = Uanis(C30) = Uanis(C31) = Uanis(C32) = Uanis(O1)
3. Others
 Fixed Sof: C31(0.5) C29(0.5) C32(0.5) C30(0.5) O1(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C7(H7), C4(H4), C5(H5), C6(H6), C15(H15), C18(H18), C16(H16),
 C17(H17)
4.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C24(H24A,H24B,H24C), C28(H28A,H28B,
 H28C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              44435
_shelx_hkl_checksum              17979
_olex2_date_sample_data_collection 2019-10-16
_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 1.201
_oxdiff_exptl_absorpt_empirical_full_min 0.866