Repurposing a supramolecular iridium catalyst <i>via</i> secondary Zn⋯O[double bond, length as m-dash]C weak interactions between the ligand and substrate leads to <i>ortho</i>-selective C(sp<sup>2</sup>)-H borylation of benzamides with unusual kinetics.
Trouvé, Jonathan; Delahaye, Vanessa; Tomasini, Michele; Rajeshwaran, Purushothaman; Roisnel, Thierry; Poater, Albert; Gramage-Doria, Rafael; Chemical science 15 (2024) 11794–11806; doi:10.1039/d4sc01515k

data_1571890
_publ_section_title
;
 Repurposing a supramolecular iridium catalyst <i>via</i> secondary
 Zn&#x22ef;O[double bond, length as m-dash]C weak interactions between the
 ligand and substrate leads to <i>ortho</i>-selective C(sp<sup>2</sup>)-H
 borylation of benzamides with unusual kinetics.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              11794
_journal_page_last               11806
_journal_paper_doi               10.1039/d4sc01515k
_journal_volume                  15
_journal_year                    2024
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C47 H35 N5 O Zn, C H2 Cl2'
_chemical_formula_sum            'C48 H37 Cl2 N5 O Zn'
_chemical_formula_weight         836.09
_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
_atom_sites_solution_secondary   difmap
_audit_update_record
;
2022-10-28 deposited with the CCDC.	2024-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                98.996(2)
_cell_angle_beta                 94.719(2)
_cell_angle_gamma                103.136(2)
_cell_formula_units_Z            2
_cell_length_a                   11.1934(5)
_cell_length_b                   12.5189(6)
_cell_length_c                   14.5833(6)
_cell_measurement_reflns_used    8431
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.40
_cell_measurement_theta_min      2.21
_cell_measurement_wavelength     0.71073
_cell_volume                     1950.79(15)
_computing_cell_refinement       'Bruker APEX2 (Bruker, 2014)'
_computing_data_collection       'Bruker APEX2 (Bruker, 2014)'
_computing_data_reduction        'Bruker APEX2 (Bruker, 2014)'
_computing_molecular_graphics
;
   'SXGRAPH (L. Farrugia, 1999), Mercury (CSD, 2020)'
;
_computing_publication_material  'CRYSCALC (T. Roisnel, local program, 2021)'
_computing_structure_refinement  'SHELXL-2018_3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'APEXII, Bruker-AXS'
_diffrn_measurement_method       'CCD rotation images, thin slices'
_diffrn_orient_matrix_UB_11      -0.0138416
_diffrn_orient_matrix_UB_12      -0.0760933
_diffrn_orient_matrix_UB_13      0.0164917
_diffrn_orient_matrix_UB_21      0.0742266
_diffrn_orient_matrix_UB_22      0.0265439
_diffrn_orient_matrix_UB_23      0.0481889
_diffrn_orient_matrix_UB_31      -0.0533200
_diffrn_orient_matrix_UB_32      0.0214392
_diffrn_orient_matrix_UB_33      0.0479499
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            21751
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.543
_diffrn_reflns_theta_min         2.406
_diffrn_source_current           30.
_diffrn_source_power             1500.0
_diffrn_source_voltage           50.
_exptl_absorpt_coefficient_mu    0.812
_exptl_absorpt_correction_T_max  0.843
_exptl_absorpt_correction_T_min  0.795
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
  [Sheldrick, G.M. (2014). SADABS Bruker AXS Inc., Madison, Wisconsin, USA]
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.370
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.210
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         8920
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0453P)^2^+0.6706P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0961
_reflns_number_gt                7539
_reflns_number_total             8920
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d4sc01515k2.cif
_cod_data_source_block           RG_GIA_022
_cod_depositor_comments          'Adding full bibliography for 1571890.cif.'
_cod_database_code               1571890
_shelx_res_checksum              62709
_shelx_hkl_checksum              4597