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_1575237
_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_absolute_configuration syn
_chemical_formula_moiety         'C19 H15 Br O'
_chemical_formula_sum            'C19 H15 Br O'
_chemical_formula_weight         339.22
_chemical_name_systematic        5-bromo-2-methoxy-1,1':4',1''-terphenyl
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-10
_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                 91.0300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.70110(10)
_cell_length_b                   12.6871(2)
_cell_length_c                   12.0065(2)
_cell_measurement_reflns_used    5962
_cell_measurement_temperature    123
_cell_measurement_theta_max      76.9710
_cell_measurement_theta_min      3.6450
_cell_volume                     1477.51(4)
_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 0.991
_diffrn_measured_fraction_theta_max 0.957
_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    -53.00  44.00   0.50    0.50    --  -45.39   0.00 -60.00  194
  2  \w    -92.00 -63.00   0.50    0.50    --  -45.39   0.00 -60.00   58
  3  \w   -136.00 -70.00   0.50    0.50    --  -46.81  28.00-150.00  132
  4  \w    -58.00  43.00   0.50    0.50    --  -46.81  28.00-150.00  202
  5  \w   -188.00 -84.00   0.50    0.50    -- -109.60  28.00-150.00  208
  6  \w   -166.00-133.00   0.50    0.50    -- -109.60   9.00  30.00   66
  7  \w   -197.00 -64.00   0.50    0.50    -- -109.60  46.00-150.00  266
  8  \w    -89.00 -53.00   0.50    0.50    -- -109.60   9.00  30.00   72
  9  \w   -180.00-155.00   0.50    0.50    -- -109.60  46.00-120.00   50
 10  \w   -196.00 -20.00   0.50    0.50    -- -109.60  18.00  90.00  352
;
_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      0.0688886000
_diffrn_orient_matrix_UB_12      0.0538577000
_diffrn_orient_matrix_UB_13      0.1017090000
_diffrn_orient_matrix_UB_21      -0.1322066000
_diffrn_orient_matrix_UB_22      -0.0167005000
_diffrn_orient_matrix_UB_23      0.0671267000
_diffrn_orient_matrix_UB_31      0.0546924000
_diffrn_orient_matrix_UB_32      -0.1074651000
_diffrn_orient_matrix_UB_33      0.0405354000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0188
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            7494
_diffrn_reflns_point_group_measured_fraction_full 0.709
_diffrn_reflns_point_group_measured_fraction_max 0.667
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.096
_diffrn_reflns_theta_min         3.484
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    3.742
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37440
_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    1.525
_exptl_crystal_description       block
_exptl_crystal_F_000             688
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexane/DCM'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.382
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 1101 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.47(3)
_refine_ls_extinction_coef       0.0030(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         4171
_refine_ls_number_restraints     83
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0514P)^2^+1.1512P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0895
_reflns_Friedel_coverage         0.390
_reflns_Friedel_fraction_full    0.425
_reflns_Friedel_fraction_max     0.376
_reflns_number_gt                4054
_reflns_number_total             4171
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01669j2.cif
_cod_data_source_block           gyp813_auto
_cod_depositor_comments
'Adding full bibliography for 1575237--1575240.cif.'
_cod_database_code               1575237
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O'
_shelx_estimated_absorpt_t_max   0.316
_shelx_estimated_absorpt_t_min   0.316
_diffrn_oxdiff_digest_frames
;
0136e158af3e6af46bd6a992d6ccdf5c51000322c4e
;
_diffrn_oxdiff_digest_hkl
;
012f7f831991f9db186b2b31e4bfd36c7a0943
;
_reflns_odcompleteness_completeness 99.17
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C32, C31, C33
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C32, C31, C30, C33, C28, C29
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C8 \\sim C9 \\sim C7: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.08
C32 \\sim C31 \\sim C33: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.08
4. Rigid body (RIGU) restrains
 C32, C31, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8, C9, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C31, C30, C29, C28, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
5.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C35(H35), C29(H29), C38(H38), C6(H6), C18(H18), C16(H16), C3(H3),
 C11(H11), C32(H32), C9(H9), C30(H30), C39(H39), C33(H33), C4(H4), C23(H23),
 C17(H17), C15(H15), C36(H36), C25(H25), C8(H8), C37(H37), C26(H26), C14(H14)
5.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C42(H42A,H42B,H42C)
;
_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 2.677
_oxdiff_exptl_absorpt_empirical_full_min 0.361