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_4518876
_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
'C50 H55 Ir2 N9 O2, 3(C F3 O3 S), H2 O, C2 H3 N'
_chemical_formula_sum            'C55 H60 F9 Ir2 N10 O12 S3'
_chemical_formula_weight         1704.71
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-05-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                83.3036(11)
_cell_angle_beta                 84.8130(12)
_cell_angle_gamma                72.8119(11)
_cell_formula_units_Z            2
_cell_length_a                   11.74509(17)
_cell_length_b                   12.84178(11)
_cell_length_c                   22.3981(3)
_cell_measurement_reflns_used    46725
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.8290
_cell_measurement_theta_min      1.6610
_cell_volume                     3199.79(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (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 0.914
_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    -63.00 118.00   1.00    5.00    --   27.49   0.00  90.00  181
  2  \w     -2.00  91.00   1.00    5.00    --   27.49-115.00 -91.00   93
  3  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00  60.00   58
  4  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00 -90.00   58
  5  \w     39.00 122.00   1.00    5.00    --   27.49 178.00 -90.00   83
  6  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00   0.00   58
  7  \w     39.00 122.00   1.00    5.00    --   27.49 178.00  90.00   83
  8  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00 120.00   58
  9  \w     39.00 122.00   1.00    5.00    --   27.49 178.00  30.00   83
 10  \w    -42.00  71.00   1.00    5.00    --   27.49 -77.00  60.00  113
 11  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00-150.00   58
 12  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00 -90.00  181
 13  \w    -15.00  32.00   1.00    5.00    --  -23.50 -99.00-120.00   47
 14  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00-120.00  181
 15  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00-180.00  181
 16  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00-150.00  181
 17  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00 -60.00   58
 18  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00 -90.00  181
 19  \w    -63.00 118.00   1.00    5.00    --   27.49   0.00 -60.00  181
 20  \w    -63.00 -24.00   1.00    5.00    --   27.49   0.00 -30.00   39
 21  \w    -16.00  42.00   1.00    5.00    --   27.49  77.00 150.00   58
;
_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      0.0436717000
_diffrn_orient_matrix_UB_12      -0.0143001000
_diffrn_orient_matrix_UB_13      0.0217638000
_diffrn_orient_matrix_UB_21      0.0452605000
_diffrn_orient_matrix_UB_22      -0.0182766000
_diffrn_orient_matrix_UB_23      -0.0227779000
_diffrn_orient_matrix_UB_31      0.0073666000
_diffrn_orient_matrix_UB_32      0.0532377000
_diffrn_orient_matrix_UB_33      -0.0052658000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            108612
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.206
_diffrn_reflns_theta_min         1.667
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.345
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82692
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
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    1.769
_exptl_crystal_description       plate
_exptl_crystal_F_000             1678
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.915
_refine_diff_density_min         -1.739
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     846
_refine_ls_number_reflns         14406
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0314P)^2^+12.8955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0812
_refine_ls_wR_factor_ref         0.0864
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12414
_reflns_number_total             14406
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00740_si_006.cif
_cod_data_source_block           20MA041_Ir-ACN
_cod_original_cell_volume        3199.79(8)
_cod_database_code               4518876
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C27H29F3Ir1N5O4S1
_shelx_estimated_absorpt_t_max   0.696
_shelx_estimated_absorpt_t_min   0.508
_diffrn_oxdiff_digest_frames
;
014a39f86bbccbb83201790902d1e617e9004688eb5
;
_diffrn_oxdiff_digest_hkl
;
01dd73346f3b8247572d4f1bf71373c48bfc92
;
_reflns_odcompleteness_completeness 99.99
_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, All O(H,H) groups
2. Restrained distances
 O9-N10
 2.95 with sigma of 0.001
 N4-N66
 1.1 with sigma of 0.001
3. Others
 Fixed Sof: N4(0.5) N66(0.5)
4.a Free rotating group:
 O7(H7A,H7B)
4.b Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C24(H24), C21(H21), C32(H32), C22(H22), C13(H13),
 C14(H14), C16(H16), C2(H2), C23(H23), C33(H33), C5(H5), C17(H17), C4(H4),
 C3(H3)
4.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C61(H61A,H61B,
 H61C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C38(H38A,H38B,H38C), C60(H60A,
 H60B,H60C), C51(H51A,H51B,H51C), C62(H62A,H62B,H62C), C41(H41A,H41B,H41C),
 C59(H59A,H59B,H59C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              6100
_shelx_hkl_checksum              56747
_olex2_date_sample_data_collection 2020-05-11
_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 1.176
_oxdiff_exptl_absorpt_empirical_full_min 0.841