Selective cleavage of unactivated arene ring C‒C bonds by iridium: key roles of benzylic C‒H activation and metal‒metal cooperativity
Tian, Yancong; Jakoobi, Martin; Boulatov, Roman; Sergeev, Alexey G.; Chemical Science 12 (2021) 3568–3579; doi:10.1039/D0SC05900E

data_1560085
_publ_section_title
;
 Selective cleavage of unactivated arene ring C--C bonds by iridium: key
 roles of benzylic C--H activation and metal--metal cooperativity
;
_journal_issue                   10
_journal_name_full               'Chemical Science'
_journal_page_first              3568
_journal_page_last               3579
_journal_paper_doi               10.1039/D0SC05900E
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C22 H33 Ir'
_chemical_formula_sum            'C22 H33 Ir'
_chemical_formula_weight         489.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-12-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2020-10-22 deposited with the CCDC.	2021-01-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.985(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.01647(19)
_cell_length_b                   16.3246(4)
_cell_length_c                   15.0490(4)
_cell_measurement_reflns_used    6815
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2070
_cell_measurement_theta_min      6.1350
_cell_volume                     1966.73(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 20.9213
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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   -101.00 -34.00   1.00    1.00    --    0.00 178.00 120.00   67
  2  \w   -101.00 -34.00   1.00    1.00    --    0.00 178.00   0.00   67
  3  \w      1.00  52.00   1.00    1.00    --    0.00 -99.00-120.00   51
  4  \w      1.00  52.00   1.00    1.00    --    0.00 -99.00  90.00   51
  5  \w     94.00 153.00   1.00    1.00    --   60.50 125.00 150.00   59
  6  \w     94.00 153.00   1.00    1.00    --   60.50 125.00-150.00   59
  7  \w     94.00 153.00   1.00    1.00    --   60.50 125.00   0.00   59
  8  \w     94.00 153.00   1.00    1.00    --   60.50 125.00 -60.00   59
  9  \w    -46.00 157.00   1.00    1.00    --   60.50  15.00 150.00  203
 10  \w     94.00 153.00   1.00    1.00    --   60.50 125.00  90.00   59
 11  \w    100.00 178.00   1.00    2.00    --  121.00 111.00 -30.00   78
 12  \w     78.00 178.00   1.00    2.00    --  121.00  50.00  60.00  100
 13  \w     78.00 178.00   1.00    2.00    --  121.00  63.00 -30.00  100
 14  \w     77.00 178.00   1.00    2.00    --  121.00  77.00  60.00  101
 15  \w    100.00 178.00   1.00    2.00    --  121.00 111.00  90.00   78
 16  \w     25.00 164.00   1.00    2.00    --  121.00 -63.00   0.00  139
 17  \w     96.00 178.00   1.00    2.00    --  121.00  80.00  90.00   82
 18  \w     57.00 150.00   1.00    2.00    --  121.00 178.00-150.00   93
 19  \w     28.00 115.00   1.00    2.00    --  121.00-111.00  30.00   87
 20  \w     28.00 115.00   1.00    2.00    --  121.00-111.00-150.00   87
 21  \w    -44.00 102.00   1.00    1.00    --    0.00  77.00   0.00  146
 22  \w    -94.00  43.00   1.00    1.00    --    0.00 -57.00  30.00  137
 23  \w   -163.00 -16.00   1.00    1.00    --  -60.50 -77.00   0.00  147
 24  \w   -163.00 -16.00   1.00    1.00    --  -60.50 -77.00 -90.00  147
 25  \w     23.00 121.00   1.00    1.00    --   60.50-125.00 -30.00   98
 26  \w     16.00 163.00   1.00    1.00    --   60.50  77.00  90.00  147
 27  \w     -2.00 154.00   1.00    1.00    --   60.50  30.00 -60.00  156
 28  \w     17.00 155.00   1.00    1.00    --   60.50  61.00-180.00  138
 29  \w     78.00 178.00   1.00    4.00    --  121.00  50.00 -60.00  100
 30  \w     28.00 115.00   1.00    4.00    --  121.00-111.00 -60.00   87
 31  \w     78.00 178.00   1.00    4.00    --  121.00  63.00 150.00  100
 32  \w     73.00 178.00   1.00    4.00    --  121.00  38.00 -90.00  105
 33  \w     77.00 178.00   1.00    4.00    --  121.00  77.00   0.00  101
 34  \w     73.00 178.00   1.00    4.00    --  121.00  38.00-150.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0492745000
_diffrn_orient_matrix_UB_12      0.0709775000
_diffrn_orient_matrix_UB_13      0.0634891000
_diffrn_orient_matrix_UB_21      -0.1729592000
_diffrn_orient_matrix_UB_22      0.0392901000
_diffrn_orient_matrix_UB_23      -0.0189078000
_diffrn_orient_matrix_UB_31      -0.0686526000
_diffrn_orient_matrix_UB_32      -0.0481152000
_diffrn_orient_matrix_UB_33      0.0782526000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            5009
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.624
_diffrn_reflns_theta_min         3.998
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.098
_exptl_absorpt_correction_T_max  1.561
_exptl_absorpt_correction_T_min  0.724
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.44a (Rigaku Oxford Diffraction, 2015)
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    1.654
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.071
_refine_diff_density_max         1.591
_refine_diff_density_min         -1.416
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     214
_refine_ls_number_reflns         5009
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0500P)^2^+8.4710P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4627
_reflns_number_total             5009
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05900e2.cif
_cod_data_source_block           as126_twin1
_cod_depositor_comments
'Adding full bibliography for 1560085--1560086.cif.'
_cod_database_code               1560085
_chemical_oxdiff_formula         'C22 H33 Ir1'
_chemical_oxdiff_usercomment     S366
_reflns_odcompleteness_completeness 98.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5285(12) 0.4715(12)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C11) = Uanis(C12)
4.a Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C18(H18A,H18B,H18C), C10(H10A,H10B,H10C), C17(H17A,H17B,
 H17C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C21(H21A,H21B,H21C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              99950
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method
'mounted on a Mitegen loop using Paratone-N oil'
_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 1.652
_oxdiff_exptl_absorpt_empirical_full_min 0.724