A cooperative electron-deficient phosphine/olefin ligand system for the site-selective mechanochemical Suzuki-Miyaura cross-coupling of 2,4-dibromoaryl ethers.
Gao, Yunpeng; Jiang, Julong; Maeda, Satoshi; Kubota, Koji; Ito, Hajime; Chemical science 16 (2025) 15964–15976; doi:10.1039/d5sc01669j

data_1575239
_publ_section_title
;
 A cooperative electron-deficient phosphine/olefin ligand system for the
 site-selective mechanochemical Suzuki-Miyaura cross-coupling of
 2,4-dibromoaryl ethers.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              15964
_journal_page_last               15976
_journal_paper_doi               10.1039/d5sc01669j
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C22 H20 O3'
_chemical_formula_sum            'C22 H20 O3'
_chemical_formula_weight         332.38
_chemical_name_systematic
'methyl 4'-methoxy-4''-methyl-[1,1':3',1''-terphenyl]-4-carboxylate'
_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             2023-02-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-10-06 deposited with the CCDC.	2025-07-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.070(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2726(5)
_cell_length_b                   34.397(2)
_cell_length_c                   7.1925(5)
_cell_measurement_reflns_used    4566
_cell_measurement_temperature    123
_cell_measurement_theta_max      30.5840
_cell_measurement_theta_min      2.3740
_cell_volume                     1642.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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      123
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.754
_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    -65.00 -39.00   0.50   17.74    --    5.00  38.00 167.00   52
  2  \w     49.00  81.00   0.50   17.74    --   -8.70  37.00   0.00   64
  3  \w    -98.00  37.00   0.50   17.74    --   -8.70  37.00   0.00  270
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1058424000
_diffrn_orient_matrix_UB_12      -0.0027569000
_diffrn_orient_matrix_UB_13      -0.0394780000
_diffrn_orient_matrix_UB_21      0.0122010000
_diffrn_orient_matrix_UB_22      -0.0123860000
_diffrn_orient_matrix_UB_23      0.0831538000
_diffrn_orient_matrix_UB_31      -0.0085669000
_diffrn_orient_matrix_UB_32      0.0162661000
_diffrn_orient_matrix_UB_33      0.0563175000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.754
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            9387
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.754
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.574
_diffrn_reflns_theta_min         2.368
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Mo) X-ray DW Source'
_exptl_absorpt_coefficient_mu    0.088
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32643
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexane/DCM'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3815
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0708P)^2^+0.5436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1170
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3328
_reflns_number_total             3815
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01669j2.cif
_cod_data_source_block           gyp906_auto
_cod_depositor_comments
'Adding full bibliography for 1575237--1575240.cif.'
_cod_database_code               1575239
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O'
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.983
_diffrn_oxdiff_digest_frames
;
015a2e9880f1eb92be2e118dfc08ae4f4c000255be2
;
_diffrn_oxdiff_digest_hkl
;
014f148361e25a3d2fd4e0096e7959d3bac724
;
_reflns_odcompleteness_completeness 97.55
_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.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C2(H2), C22(H22), C3(H3), C11(H11), C9(H9), C8(H8), C18(H18),
 C21(H21), C19(H19), C12(H12)
2.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C15(H15A,H15B,H15C), C25(H25A,H25B,H25C)
;
_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 2.465
_oxdiff_exptl_absorpt_empirical_full_min 0.472