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_1575240
_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         'C46 H43 Br2 F12 O3 P Pd'
_chemical_formula_sum            'C46 H43 Br2 F12 O3 P Pd'
_chemical_formula_weight         1168.99
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-17
_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                 90.8490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.15180(10)
_cell_length_b                   19.28590(10)
_cell_length_c                   18.4290(2)
_cell_measurement_reflns_used    19035
_cell_measurement_temperature    123
_cell_measurement_theta_max      77.1780
_cell_measurement_theta_min      2.2860
_cell_volume                     4673.90(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_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                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.908
_diffrn_measured_fraction_theta_max 0.863
_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   -116.00 -90.00   0.50    0.50    --  -46.97  28.00  11.00   52
  2  \w    -47.00  13.00   0.50    0.50    --  -46.97  28.00  11.00  120
  3  \w   -141.00 -95.00   0.50    1.36    -- -109.60  28.00  11.00   92
  4  \w    -65.00 -22.00   0.50    1.36    -- -109.60  28.00  11.00   86
  5  \w     13.00  39.00   0.50    0.50    --    5.00  28.00  11.00   52
  6  \w     60.00  86.00   0.50    0.50    --    5.00   9.00-150.00   52
  7  \w    -71.00 -45.00   0.50    0.50    --  -45.63  28.00  11.00   52
  8  \w   -136.00  -1.00   0.50    0.50    --  -46.97  18.00 150.00  270
  9  \w   -189.00-135.00   0.50    1.36    -- -109.60  28.00-180.00  108
 10  \w   -118.00 -20.00   0.50    1.36    -- -109.60  28.00-180.00  196
 11  \w   -189.00 -56.00   0.50    1.36    -- -109.60  46.00-180.00  266
 12  \w   -137.00-112.00   0.50    1.36    -- -109.60   0.00-180.00   50
 13  \w   -197.00-172.00   0.50    1.36    -- -109.60   0.00-180.00   50
 14  \w    -53.00 -28.00   0.50    1.36    -- -109.60  46.00-180.00   50
;
_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      0.0829593000
_diffrn_orient_matrix_UB_12      0.0559701000
_diffrn_orient_matrix_UB_13      -0.0069934000
_diffrn_orient_matrix_UB_21      -0.0693621000
_diffrn_orient_matrix_UB_22      0.0528195000
_diffrn_orient_matrix_UB_23      0.0378413000
_diffrn_orient_matrix_UB_31      0.0450940000
_diffrn_orient_matrix_UB_32      -0.0215037000
_diffrn_orient_matrix_UB_33      0.0741808000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.908
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21110
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.313
_diffrn_reflns_theta_min         3.317
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    6.310
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35551
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.661
_exptl_crystal_description       block
_exptl_crystal_F_000             2328
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pentane/DCM'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.445
_refine_diff_density_min         -1.658
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     625
_refine_ls_number_reflns         8572
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0985P)^2^+9.9825P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1442
_refine_ls_wR_factor_ref         0.1488
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8420
_reflns_number_total             8572
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01669j2.cif
_cod_data_source_block           gyp919
_cod_depositor_comments
'Adding full bibliography for 1575237--1575240.cif.'
_cod_database_code               1575240
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O P Pd F Br'
_shelx_estimated_absorpt_t_max   0.253
_shelx_estimated_absorpt_t_min   0.187
_reflns_odcompleteness_completeness 90.57
_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 body (RIGU) restrains
 C22A, C23A, C01T, C01S, C23, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C01T)=Sof(H01Z)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C01S)=Sof(H01Y)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C011(H011), C01I(H01I), C01S(H01Y), C01T(H01Z)
4.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C00F(H00F), C00I(H00I), C00T(H00T), C00Y(H00Y), C012(H012),
 C014(H014), C015(H015), C016(H016), C017(H017), C018(H018), C01A(H01A),
 C01B(H01B)
4.c Idealised Me refined as rotating group:
 C01D(H01C,H01D,H01E), C01F(H01F,H01G,H01H), C01J(H01J,H01K,H01L), C01K(H01M,
 H01N,H01O), C01M(H01P,H01Q,H01R), C01P(H01S,H01T,H01U), C01Q(H01V,H01W,H01X),
 C23(H23A,H23B,H23C), C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F), C23A(H23D,H23E,
 H23F)
;
_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 3.622
_oxdiff_exptl_absorpt_empirical_full_min 0.267