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_4518875
_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         'C24 H27 Ir N4 O, C4 O'
_chemical_formula_sum            'C28 H27 Ir N4 O2'
_chemical_formula_weight         643.73
_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             2019-10-31
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 131.483(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3205(2)
_cell_length_b                   24.9862(2)
_cell_length_c                   15.3632(3)
_cell_measurement_reflns_used    21454
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      77.1080
_cell_measurement_theta_min      3.5390
_cell_volume                     2680.35(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.980
_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    -91.00 -35.00   0.50    0.50    --  -18.75 176.00  88.00  112
  2  \w    -60.00  -1.00   0.50    0.50    --  -18.75 114.00 -49.00  118
  3  \w    -90.00 -39.00   0.50    0.50    --  -18.75-176.00  81.00  102
  4  \w     24.00  91.00   0.50    0.50    --   48.53-114.00-140.00  134
  5  \w     99.00 174.00   0.50    1.25    --  107.16 114.00 -49.00  150
  6  \w     35.00 112.00   0.50    1.25    --  107.16-114.00-140.00  154
  7  \w    -66.00  -9.00   0.50    0.50    --  -18.75 125.00  60.00  114
  8  \w    -25.00  23.00   0.50    0.50    --   48.53 -19.00-120.00   96
  9  \w    -25.00  23.00   0.50    0.50    --   48.53 -19.00 -90.00   96
 10  \w    -25.00  23.00   0.50    0.50    --   48.53 -19.00-150.00   96
 11  \w    -24.00  40.00   0.50    0.50    --   48.53 -38.00-180.00  128
 12  \w    -25.00  23.00   0.50    0.50    --   48.53 -19.00 120.00   96
 13  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00-120.00   54
 14  \w     95.00 174.00   0.50    1.25    --  107.16  19.00 120.00  158
 15  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00 -30.00   54
 16  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00-180.00   54
 17  \w     93.00 174.00   0.50    1.25    --  107.16  57.00 120.00  162
 18  \w     95.00 174.00   0.50    1.25    --  107.16  19.00 -60.00  158
 19  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00 -90.00   54
 20  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00 -60.00   54
 21  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00-150.00   54
 22  \w     35.00 110.00   0.50    1.25    --  107.16 -99.00 -90.00  150
 23  \w     35.00 102.00   0.50    1.25    --  107.16 -77.00 -60.00  134
 24  \w     35.00 117.00   0.50    1.25    --  107.16-125.00 -60.00  164
 25  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00  90.00   54
 26  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00 120.00   54
 27  \w     36.00  62.00   0.50    1.25    --  107.16 -57.00  30.00   52
 28  \w     66.00 101.00   0.50    1.25    --  107.16 -77.00-180.00   70
 29  \w     35.00  62.00   0.50    1.25    --  107.16 -57.00  60.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0199411000
_diffrn_orient_matrix_UB_12      0.0050906000
_diffrn_orient_matrix_UB_13      -0.1075670000
_diffrn_orient_matrix_UB_21      -0.0369132000
_diffrn_orient_matrix_UB_22      0.0605163000
_diffrn_orient_matrix_UB_23      -0.0052860000
_diffrn_orient_matrix_UB_31      0.2165320000
_diffrn_orient_matrix_UB_32      0.0106949000
_diffrn_orient_matrix_UB_33      0.0794512000
_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  0.0254
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            26394
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.487
_diffrn_reflns_theta_min         3.538
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.885
_exptl_absorpt_correction_T_max  0.807
_exptl_absorpt_correction_T_min  0.522
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.595
_exptl_crystal_description       block
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.103
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.769
_refine_diff_density_min         -1.562
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         5587
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0296
_refine_ls_R_factor_gt           0.0287
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0190P)^2^+8.3782P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0655
_refine_ls_wR_factor_ref         0.0660
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5418
_reflns_number_total             5587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00740_si_005.cif
_cod_data_source_block           19ma116_absorption
_cod_original_cell_volume        2680.35(15)
_cod_database_code               4518875
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C34 H28 Ir1 N4 O2 '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid body (RIGU) restrains
 Ir1, H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: O2(0.5) O3(0.5)
 Fixed Uiso: H(0.05)
4.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C13(H13)
4.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C22(H22A,H22B,H22C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              78553
_shelx_hkl_checksum              38098
_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 1.762
_oxdiff_exptl_absorpt_empirical_full_min 0.681