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_1560086
_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         'C20 H23 Ir'
_chemical_formula_sum            'C20 H23 Ir'
_chemical_formula_weight         455.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-27
_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                 97.5244(17)
_cell_angle_gamma                90
_cell_formula_units_Z            32
_cell_length_a                   22.2884(4)
_cell_length_b                   22.2818(4)
_cell_length_c                   26.1267(5)
_cell_measurement_reflns_used    24800
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.4760
_cell_measurement_theta_min      2.8960
_cell_volume                     12863.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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 5.2303
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.911
_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    -20.00  47.00   1.00   30.00    --    8.40 -99.00 -60.00   67
  2  \w    -35.00  58.00   1.00   30.00    --  -10.27  57.00-180.00   93
  3  \w    -35.00  58.00   1.00   30.00    --  -10.27  57.00  60.00   93
  4  \w    -20.00  28.00   1.00   30.00    --  -10.27 -99.00-120.00   48
  5  \w    -81.00 -29.00   1.00   30.00    --  -10.27 -38.00 120.00   52
  6  \w    -82.00  20.00   1.00   30.00    --  -10.27 -77.00  60.00  102
  7  \w    -25.00   1.00   1.00   30.00    --  -10.27 -38.00 -30.00   26
  8  \w    -19.00   7.00   1.00   30.00    --  -10.27 -81.00 148.00   26
;
_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      0.0212551000
_diffrn_orient_matrix_UB_12      0.0238684000
_diffrn_orient_matrix_UB_13      0.0025311000
_diffrn_orient_matrix_UB_21      -0.0155366000
_diffrn_orient_matrix_UB_22      0.0138385000
_diffrn_orient_matrix_UB_23      -0.0223496000
_diffrn_orient_matrix_UB_31      -0.0183639000
_diffrn_orient_matrix_UB_32      0.0159016000
_diffrn_orient_matrix_UB_33      0.0155999000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            96652
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.852
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.773
_diffrn_reflns_theta_min         2.411
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.295
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92803
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
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    1.882
_exptl_crystal_description       prism
_exptl_crystal_F_000             7040
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.557
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 9149 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.015(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1553
_refine_ls_number_reflns         31301
_refine_ls_number_restraints     388
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0264
_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^)+(0.0172P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0473
_refine_ls_wR_factor_ref         0.0530
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.793
_reflns_number_gt                23383
_reflns_number_total             31301
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05900e2.cif
_cod_data_source_block           as124
_cod_depositor_comments
;
Adding full bibliography for 1560085--1560086.cif.

2022-06-21
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C40 H46 Ir2'
_cod_original_formula_weight         911.17
_cod_original_formula_moiety         '2(C20 H23 Ir)'
_cod_original_formula_units_Z            16
_cod_database_code               1560086
_chemical_oxdiff_formula         'C20 H23 Ir1'
_chemical_oxdiff_usercomment     S347
_reflns_odcompleteness_completeness 99.90
_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. Rigid bond restraints
 C1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1A, C2A, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1B, C2B, C3B, C4B, C5B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1C, C2C, C3C, C4C, C5C
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1D, C2D, C3D, C4D, C5D
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1E, C2E, C3E, C4E, C5E
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1F, C2F, C3F, C4F, C5F
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1G, C2G, C3G, C4G, C5G
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1B \\sim C2B \\sim C3B \\sim C4B \\sim C5B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1C \\sim C2C \\sim C3C \\sim C4C \\sim C5C: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1D \\sim C2D \\sim C3D \\sim C4D \\sim C5D: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1E \\sim C2E \\sim C3E \\sim C4E \\sim C5E: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1F \\sim C2F \\sim C3F \\sim C4F \\sim C5F: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1G \\sim C2G \\sim C3G \\sim C4G \\sim C5G: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(C4C)
\\sim Ueq, Uanis(C4D) \\sim Ueq, Uanis(C4E) \\sim Ueq, Uanis(C4F) \\sim Ueq,
Uanis(C4G) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C14A) \\sim Ueq, Uanis(C20D) \\sim Ueq, Uanis(C11D) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C19(H19), C20(H20), C11D(H11D), C12D(H12D), C19D(H19D),
 C20D(H20D), C11F(H11F), C12F(H12F), C19F(H19F), C20F(H20F), C11A(H11A),
 C12A(H12A), C19A(H19A), C20A(H20A), C11E(H11E), C12E(H12E), C19E(H19E),
 C20E(H20E), C11B(H11B), C12B(H12B), C19B(H19B), C20B(H20B), C11C(H11C),
 C12C(H12C), C19C(H19C), C20C(H20C), C11G(H11G), C12G(H12G), C19G(H19G),
 C20G(H20G)
4.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C14D(H14D), C15D(H15D), C16D(H16D),
 C17D(H17D), C14F(H14F), C15F(H15F), C16F(H16F), C17F(H17F), C14A(H14A),
 C15A(H15A), C16A(H16A), C17A(H17A), C14E(H14E), C15E(H15E), C16E(H16E),
 C17E(H17E), C14B(H14B), C15B(H15B), C16B(H16B), C17B(H17B), C14C(H14C),
 C15C(H15C), C16C(H16C), C17C(H17C), C14G(H14G), C15G(H15G), C16G(H16G),
 C17G(H17G)
4.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C6D(H6DA,H6DB,H6DC), C7D(H7DA,H7DB,H7DC), C8D(H8DA,H8DB,H8DC),
 C9D(H9DA,H9DB,H9DC), C10D(H10D,H10E,H10F), C6F(H6FA,H6FB,H6FC), C7F(H7FA,H7FB,
 H7FC), C8F(H8FA,H8FB,H8FC), C9F(H9FA,H9FB,H9FC), C10F(H10G,H10H,H10I),
 C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10J,H10K,H10L), C6E(H6EA,H6EB,H6EC), C7E(H7EA,H7EB,H7EC),
 C8E(H8EA,H8EB,H8EC), C9E(H9EA,H9EB,H9EC), C10E(H10M,H10N,H10O), C6B(H6BA,H6BB,
 H6BC), C7B(H7BA,H7BB,H7BC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC),
 C10B(H10P,H10Q,H10R), C6C(H6CA,H6CB,H6CC), C7C(H7CA,H7CB,H7CC), C8C(H8CA,H8CB,
 H8CC), C9C(H9CA,H9CB,H9CC), C10C(H10S,H10T,H10U), C6G(H6GA,H6GB,H6GC),
 C7G(H7GA,H7GB,H7GC), C8G(H8GA,H8GB,H8GC), C9G(H9GA,H9GB,H9GC), C10G(H10V,H10W,
 H10X)
;
_shelx_res_checksum              69082
_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 1.127
_oxdiff_exptl_absorpt_empirical_full_min 0.890