CH Bond-activation in aromatic ketones mediated by Iridium-Tris(pyrazolyl) borate complexes
Ortiz-Hernández, Mariana; Salazar, Verónica; Mendoza-Espinosa, Daniel; Gomez-Bonilla, Manuel Alejandro; Cristobal, Crispin; Ortega-Alfaro, M. Carmen; Suárez, Andrés; Sandoval-Chavez, Cesar; Dalton Transactions  (2023) –; doi:10.1039/D3DT02849F

data_7714446
_publ_section_title
;
 CH Bond-activation in aromatic ketones mediated by
 Iridium-Tris(pyrazolyl) borate complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02849F
_journal_year                    2023
_chemical_formula_moiety         'C60 H66 B2 F6 Ir2 N12 O2'
_chemical_formula_sum            'C60 H66 B2 F6 Ir2 N12 O2'
_chemical_formula_weight         1507.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-30 deposited with the CCDC.	2023-11-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.513(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.8262(2)
_cell_length_b                   24.3511(5)
_cell_length_c                   15.4932(4)
_cell_measurement_reflns_used    57816
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.4210
_cell_measurement_theta_min      3.3920
_cell_volume                     3319.59(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3659
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_details
;
  1 omega  -84.00   14.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  -37.0000 -120.0000 98

  2 omega  -83.00   18.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  -57.0000  150.0000 101

  3 omega  -38.00   63.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610   57.0000 -150.0000 101

  4 omega  -38.00   63.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610   57.0000  -60.0000 101

  5 omega  -25.00   52.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672  -99.0000   60.0000 77

  6 omega  -21.00   88.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672   77.0000   60.0000 109

  7 omega   14.00   87.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672 -153.0000 -154.5219 73

  8 omega  -86.00  -37.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  155.0000  111.5861 49

  9 omega  -85.00  -36.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  153.0000  161.3962 49

 10 omega  -67.00  -19.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  126.0000  -63.3632 48

 11 omega  -65.00  -17.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       -9.9610  123.0000  174.2835 48

 12 omega   -6.00   65.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672 -121.0000  -41.0000 71

 13 omega   -2.00   69.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       12.0000 -126.0000  108.1115 71

 14 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000 -180.0000 177

 15 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000 -150.0000 177

 16 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000 -120.0000 177

 17 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000  -90.0000 177

 18 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000  -60.0000 177

 19 omega  -63.00   44.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       12.0000  -73.0000  -26.1400 107

 20 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000    0.0000 177

 21 omega  -77.00   36.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000   30.0000 113

 22 omega  -77.00  100.00   1.0000   24.1950
omega____ theta____ kappa____ phi______ frames
    -       11.3672    0.0000  -30.0000 177
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0057108000
_diffrn_orient_matrix_UB_12      0.0289702000
_diffrn_orient_matrix_UB_13      -0.0037318000
_diffrn_orient_matrix_UB_21      0.0599472000
_diffrn_orient_matrix_UB_22      0.0000204000
_diffrn_orient_matrix_UB_23      -0.0279215000
_diffrn_orient_matrix_UB_31      -0.0535930000
_diffrn_orient_matrix_UB_32      -0.0030282000
_diffrn_orient_matrix_UB_33      -0.0362692000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0925
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            233589
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.907
_diffrn_reflns_theta_min         2.878
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.070
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       Block
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.746
_refine_diff_density_min         -0.836
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     414
_refine_ls_number_reflns         9127
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0349
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0402P)^2^+6.6607P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0798
_refine_ls_wR_factor_ref         0.0928
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7063
_reflns_number_total             9127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02849f2.cif
_cod_data_source_block           dme-51
_cod_database_code               7714446
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C12 H26 N5 Ir F'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F2-F1 \\sim F2-F3 \\sim F1-F3 \\sim F1A-F3A \\sim F1A-F2A \\sim F3A-F2A
 with sigma of 0.04
 C28-C25 \\sim C28-F2 \\sim C28-F1 \\sim C28-F3 \\sim C28-F1A \\sim C28-F3A
\\sim C28-F2A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F2, F1, F3, C28, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, F3A, F2A, C28, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F1A)=Sof(F3A)=Sof(F2A)=1-FVAR(1)
 Sof(F2)=Sof(F1)=Sof(F3)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 B1(H1)
5.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C23(H23), C24(H24), C2(H2), C7(H7), C21(H21), C17(H17), C12(H12),
 C20(H20), C18(H18), C19(H19)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C15(H15A,H15B,H15C), C30(H30A,H30B,H30C), C10(H10A,H10B,
 H10C), C4(H4A,H4B,H4C), C9(H9A,H9B,H9C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              79998
_shelx_fab_checksum              26858
_olex2_submission_special_instructions 'No special instructions were received'