Heterolytic cleavage of a Si-H bond by a metal-ligand cooperation of a cationic iridium amido complex and hydrosilylation of aldehydes.
Iizuka, Kosuke; Nakajima, Yumiko; Sato, Kazuhiko; Dalton transactions (Cambridge, England : 2003) 51 (2022) 12781–12785; doi:10.1039/d2dt01733d

data_7711431
_publ_section_title
;
 Heterolytic cleavage of a Si-H bond by a metal-ligand cooperation of a
 cationic iridium amido complex and hydrosilylation of aldehydes.
;
_journal_issue                   34
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12781
_journal_page_last               12785
_journal_paper_doi               10.1039/d2dt01733d
_journal_volume                  51
_journal_year                    2022
_chemical_formula_moiety         'C30 H44 Ir N3 O4 Si, C F3 O3 S'
_chemical_formula_sum            'C31 H44 F3 Ir N3 O7 S Si'
_chemical_formula_weight         880.04
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-07-09 deposited with the CCDC.	2022-08-02 downloaded from the CCDC.
;
_cell_angle_alpha                104.111(2)
_cell_angle_beta                 91.708(2)
_cell_angle_gamma                113.962(2)
_cell_formula_units_Z            2
_cell_length_a                   11.3688(3)
_cell_length_b                   11.7329(3)
_cell_length_c                   15.0057(3)
_cell_measurement_reflns_used    10572
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      74.8790
_cell_measurement_theta_min      3.0380
_cell_volume                     1755.06(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_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     41.00  70.00   0.50    0.37    --   65.29-143.00  70.00   58
  2  \w     69.00 104.00   0.50    0.37    --   69.62-143.00  70.00   70
  3  \w     47.00  73.00   0.50    0.37    --   65.29-125.00   0.00   52
  4  \w     43.00  82.00   0.50    0.37    --   65.29-125.00 -60.00   78
  5  \w     57.00  96.00   0.50    0.37    --   69.62-127.00-119.00   78
  6  \w     34.00  59.00   0.50    0.37    --   65.29-127.00-119.00   50
  7  \w     25.00  59.00   0.50    0.37    --   65.29-125.00 120.00   68
  8  \w     41.00 102.00   0.50    0.37    --   65.29  15.00   0.00  122
  9  \w     39.00  99.00   0.50    0.37    --   65.29  15.00 -60.00  120
 10  \w     41.00 102.00   0.50    0.37    --   65.29  15.00-120.00  122
 11  \w   -107.00 -60.00   0.50    0.37    --  -80.50 164.00 -11.54   94
 12  \w    -71.00 -46.00   0.50    0.37    --  -80.50 136.00  63.35   50
 13  \w    -64.00 -39.00   0.50    0.37    --  -80.50 132.00  99.76   50
 14  \w    -95.00 -69.00   0.50    0.37    --  -80.50 132.00  99.76   52
 15  \w    -91.00 -66.00   0.50    0.37    --  -65.46 143.00 125.00   50
 16  \w   -111.00 -63.00   0.50    0.37    --  -80.50 135.00 162.25   96
 17  \w    -93.00 -66.00   0.50    0.37    --  -78.66 143.00 125.00   54
 18  \w    -59.00 -34.00   0.50    0.37    --  -65.46 127.00 -44.00   50
 19  \w    -87.00 -61.00   0.50    0.37    --  -76.07 127.00 -44.00   52
 20  \w   -109.00 -83.00   0.50    0.37    --  -80.50 129.00-125.40   52
 21  \w   -106.00 -80.00   0.50    0.37    --  -78.66 127.00 -44.00   52
 22  \w   -107.00 -81.00   0.50    0.37    --  -80.50 126.00 -28.98   52
 23  \w   -105.00 -79.00   0.50    0.37    --  -78.66 125.00-150.00   52
 24  \w    -59.00 -34.00   0.50    0.37    --  -76.07 125.00   0.00   50
 25  \w   -102.00 -64.00   0.50    0.37    --  -76.07 125.00   0.00   76
 26  \w   -105.00 -40.00   0.50    0.37    --  -78.66 125.00 -60.00  130
 27  \w    -83.00 -38.00   0.50    0.37    --  -78.66 125.00   0.00   90
 28  \w    -88.00 -36.00   0.50    0.37    --  -65.46 125.00  60.00  104
 29  \w    -68.00 -42.00   0.50    0.37    --  -80.50 123.00  82.78   52
 30  \w   -106.00 -73.00   0.50    0.37    --  -80.50 123.00  82.78   66
 31  \w   -106.00 -80.00   0.50    0.37    --  -80.50 125.00 129.94   52
 32  \w    -75.00 -41.00   0.50    0.37    --  -80.50 125.00 129.94   68
 33  \w   -102.00 -48.00   0.50    0.37    --  -80.50 115.00 168.72  108
 34  \w    -99.00 -67.00   0.50    0.37    --  -80.50 122.00  53.46   64
 35  \w   -105.00 -43.00   0.50    0.37    --  -80.50 121.00  27.21  124
 36  \w   -104.00 -78.00   0.50    0.37    --  -80.50 119.00 -69.90   52
 37  \w    -94.00 -42.00   0.50    0.37    --  -80.50 118.00 -72.98  104
 38  \w    -95.00 -51.00   0.50    0.37    --  -76.00 112.00-115.35   88
 39  \w    -75.00 -49.00   0.50    0.37    --  -80.50  79.00 -98.66   52
 40  \w    -72.00 -47.00   0.50    0.37    --  -80.50  73.00-123.84   50
 41  \w    -71.00 -46.00   0.50    0.37    --  -80.50  71.00 -39.52   50
 42  \w    -71.00 -45.00   0.50    0.37    --  -80.50  72.00  21.64   52
 43  \w    -69.00 -44.00   0.50    0.37    --  -80.50  63.00 145.17   50
 44  \w    -70.00 -44.00   0.50    0.37    --  -80.50  67.00 171.03   52
 45  \w   -101.00 -45.00   0.50    0.37    --  -76.07   0.00  60.00  112
 46  \w   -113.00 -45.00   0.50    0.37    --  -78.66   0.00-150.00  136
 47  \w   -119.00 -55.00   0.50    0.37    --  -78.66 -15.00 -60.00  128
 48  \w   -119.00 -94.00   0.50    0.37    --  -80.50 -57.00  25.58   50
 49  \w   -117.00 -92.00   0.50    0.37    --  -80.50 -69.00  61.07   50
 50  \w   -113.00 -88.00   0.50    0.37    --  -80.50 -76.00  73.62   50
 51  \w   -122.00 -97.00   0.50    0.37    --  -80.50 -54.00 137.85   50
 52  \w   -121.00 -96.00   0.50    0.37    --  -80.50 -45.00 144.68   50
 53  \w   -122.00 -97.00   0.50    0.37    --  -80.50 -54.00  91.33   50
 54  \w   -123.00 -97.00   0.50    0.37    --  -80.50 -40.00  93.29   52
 55  \w   -123.00 -98.00   0.50    0.37    --  -80.50 -44.00 -64.37   50
 56  \w   -125.00-100.00   0.50    0.37    --  -80.50 -41.00 -87.50   50
 57  \w   -118.00 -51.00   0.50    0.37    --  -78.66 -15.00-180.00  134
 58  \w   -123.00 -98.00   0.50    0.37    --  -80.50 -39.00-145.03   50
 59  \w   -112.00 -87.00   0.50    0.37    --  -80.50 -90.00 -78.32   50
 60  \w   -107.00 -71.00   0.50    0.37    --  -78.66-143.00  70.00   72
 61  \w   -107.00 -67.00   0.50    0.37    --  -80.50-163.00  95.41   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1139824000
_diffrn_orient_matrix_UB_12      -0.0384605000
_diffrn_orient_matrix_UB_13      -0.0143213000
_diffrn_orient_matrix_UB_21      0.0426130000
_diffrn_orient_matrix_UB_22      0.0452928000
_diffrn_orient_matrix_UB_23      0.1058462000
_diffrn_orient_matrix_UB_31      -0.0875037000
_diffrn_orient_matrix_UB_32      -0.1373804000
_diffrn_orient_matrix_UB_33      0.0062480000
_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  0.0638
_diffrn_reflns_av_unetI/netI     0.0673
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            26808
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.240
_diffrn_reflns_theta_min         3.069
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.808
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.666
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       plate
_exptl_crystal_F_000             882
_exptl_crystal_size_max          0.059
_exptl_crystal_size_mid          0.049
_exptl_crystal_size_min          0.008
_refine_diff_density_max         1.640
_refine_diff_density_min         -1.486
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         6241
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0470
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0609P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1043
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5095
_reflns_number_total             6241
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01733d2.cif
_cod_data_source_block           aist
_cod_original_cell_volume        1755.05(8)
_cod_database_code               7711431
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C32 H44 F3 Ir1 N2 O7 S1 Si1'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.625
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 Ir1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(Ir1A)=1-FVAR(1)
 Sof(Ir1)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C11(H11A,H11B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C17(H17), C18(H18)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              32613
_shelx_hkl_checksum              83077
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   6350
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.185
_oxdiff_exptl_absorpt_empirical_full_min 0.669