Selective, radical-free activation of benzylic C-H bonds in methylarenes.
Chan, Antony P. Y.; Jakoobi, Martin; Wang, Chenxu; Tian, Yancong; Halcovitch, Nathan; Boulatov, Roman; Sergeev, Alexey G.; Chemical communications (Cambridge, England) 57 (2021) 7894–7897; doi:10.1039/d1cc03445f

data_7128641
_publ_section_title
;
 Selective, radical-free activation of benzylic C-H bonds in methylarenes.
;
_journal_issue                   64
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              7894
_journal_page_last               7897
_journal_paper_doi               10.1039/d1cc03445f
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C35 H37 Ir P'
_chemical_formula_sum            'C35 H37 Ir P'
_chemical_formula_weight         680.81
_chemical_properties_physical    Air-sensitive
_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
_audit_creation_date             2020-03-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-06-17 deposited with the CCDC.	2021-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                75.957(2)
_cell_angle_beta                 68.820(3)
_cell_angle_gamma                62.077(3)
_cell_formula_units_Z            2
_cell_length_a                   10.9650(3)
_cell_length_b                   11.3610(3)
_cell_length_c                   14.1758(4)
_cell_measurement_reflns_used    25832
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.0230
_cell_measurement_theta_min      4.4030
_cell_volume                     1449.14(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2282
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -70.00  34.00   1.00    5.00    --  -40.17  57.00-150.00  104
  2  \w   -116.00 -14.00   1.00    5.00    --  -40.17 -38.00  60.00  102
  3  \w    -92.00  -2.00   1.00    5.00    --  -40.17 125.00 -90.00   90
  4  \w   -116.00 -14.00   1.00    5.00    --  -40.17 -38.00 -30.00  102
  5  \w    -92.00  -2.00   1.00    5.00    --  -40.17 125.00-120.00   90
  6  \w     23.00  97.00   1.00    5.00    --   40.17-125.00  90.00   74
  7  \w    100.00 178.00   1.00   20.00    --  113.00 111.00 -90.00   78
  8  \w     57.00 150.00   1.00   20.00    --  113.00 178.00 -90.00   93
  9  \w    100.00 178.00   1.00   20.00    --  113.00 111.00-180.00   78
 10  \w    100.00 178.00   1.00   20.00    --  113.00 111.00  60.00   78
 11  \w     29.00 110.00   1.00   20.00    --  113.00 -94.00   0.00   81
 12  \w     52.00 178.00   1.00   20.00    --  113.00  15.00   0.00  126
 13  \w     29.00 110.00   1.00   20.00    --  113.00 -94.00  60.00   81
 14  \w     35.00 113.00   1.00   20.00    --  113.00-111.00 -60.00   78
 15  \w     35.00 113.00   1.00   20.00    --  113.00-111.00 150.00   78
 16  \w     35.00 113.00   1.00   20.00    --  113.00-111.00 120.00   78
 17  \w     35.00 113.00   1.00   20.00    --  113.00-111.00  60.00   78
 18  \w     79.00 178.00   1.00   20.00    --  113.00  77.00   0.00   99
 19  \w     79.00 178.00   1.00   20.00    --  113.00  77.00 -60.00   99
 20  \w     35.00 144.00   1.00   20.00    --  113.00 -30.00 -60.00  109
 21  \w     29.00 110.00   1.00   20.00    --  113.00 -94.00 -30.00   81
 22  \w    100.00 178.00   1.00   20.00    --  113.00 111.00   0.00   78
 23  \w     35.00 113.00   1.00   20.00    --  113.00-111.00 -30.00   78
 24  \w     83.00 178.00   1.00   20.00    --  113.00  61.00-120.00   95
 25  \w     29.00 110.00   1.00   20.00    --  113.00 -94.00-150.00   81
 26  \w     83.00 178.00   1.00   20.00    --  113.00  61.00 120.00   95
 27  \w   -114.00 -11.00   1.00    5.00    --  -40.17 -57.00-150.00  103
 28  \w   -119.00  -7.00   1.00    5.00    --  -40.17 -77.00 -60.00  112
 29  \w    -34.00  70.00   1.00    5.00    --   40.17 -57.00  30.00  104
 30  \w      7.00 119.00   1.00    5.00    --   40.17  77.00  60.00  112
 31  \w      1.00  27.00   1.00    5.00    --   40.17  93.00 -93.39   26
 32  \w      7.00 119.00   1.00    5.00    --   40.17  77.00 150.00  112
 33  \w     83.00 178.00   1.00   20.00    --  113.00  61.00  60.00   95
 34  \w     83.00 178.00   1.00   20.00    --  113.00  61.00 -90.00   95
 35  \w     79.00 178.00   1.00   20.00    --  113.00  77.00 -30.00   99
 36  \w     83.00 178.00   1.00   20.00    --  113.00  61.00 150.00   95
 37  \w     79.00 178.00   1.00   20.00    --  113.00  77.00 120.00   99
 38  \w     83.00 178.00   1.00   20.00    --  113.00  61.00  90.00   95
 39  \w     79.00 178.00   1.00   20.00    --  113.00  77.00  30.00   99
 40  \w     79.00 178.00   1.00   20.00    --  113.00  77.00-180.00   99
 41  \w     79.00 178.00   1.00   20.00    --  113.00  77.00-120.00   99
 42  \w     83.00 158.00   1.00   20.00    --  113.00  61.00-150.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1427123000
_diffrn_orient_matrix_UB_12      0.0746242000
_diffrn_orient_matrix_UB_13      -0.0282449000
_diffrn_orient_matrix_UB_21      -0.0754890000
_diffrn_orient_matrix_UB_22      -0.0606565000
_diffrn_orient_matrix_UB_23      0.0996859000
_diffrn_orient_matrix_UB_31      -0.0390162000
_diffrn_orient_matrix_UB_32      0.1203871000
_diffrn_orient_matrix_UB_33      0.0543811000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            31991
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.317
_diffrn_reflns_theta_min         3.357
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.585
_exptl_absorpt_correction_T_max  0.64135
_exptl_absorpt_correction_T_min  0.61453
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.560
_exptl_crystal_description       plate
_exptl_crystal_F_000             678
_exptl_crystal_size_max          0.067
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.037
_exptl_crystal_size_rad          0.034
_refine_diff_density_max         1.189
_refine_diff_density_min         -0.988
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         6029
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0179
_refine_ls_R_factor_gt           0.0174
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0336P)^2^+0.7859P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0483
_refine_ls_wR_factor_ref         0.0486
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5896
_reflns_number_total             6029
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc03445f2.cif
_cod_data_source_block           as136
_cod_depositor_comments          'Adding full bibliography for 7128641.cif.'
_cod_database_code               7128641
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C70 H74 Ir2 P2'
_chemical_oxdiff_usercomment     AC175A
_diffrn_oxdiff_digest_frames
;
0109ef88acd18448bfa5d518507b336098038233cb9
;
_diffrn_oxdiff_digest_hkl
;
01cf6706f9557e76237766ba35418b1b9a80ab
;
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
2.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)
;
_shelx_res_checksum              50878
_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 1.732
_oxdiff_exptl_absorpt_empirical_full_min 0.805