Mechanistic Studies of the Palladium-Catalyzed Desulfinative Cross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts.
de Gombert, Antoine; McKay, Alasdair I.; Davis, Christopher J.; Wheelhouse, Katherine M.; Willis, Michael C.; Journal of the American Chemical Society 142 (2020) 3564–3576; doi:10.1021/jacs.9b13260

data_4134146
_publ_section_title
;
 Mechanistic Studies of the Palladium-Catalyzed Desulfinative
 Cross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts.
;
_journal_issue                   7
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3564
_journal_page_last               3576
_journal_paper_doi               10.1021/jacs.9b13260
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C47.95 H75.95 Br0.15 F O1.7 P2 Pd S0.85'
_chemical_formula_sum            'C47.95 H75.95 Br0.15 F O1.7 P2 Pd S0.85'
_chemical_formula_weight         906.21
_chemical_name_common            (4-F-C6H4)Pd(PCy3)2(SO2C6H4Me)
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7818(3)
_cell_length_b                   13.9735(4)
_cell_length_c                   33.9579(9)
_cell_measurement_reflns_used    9691
_cell_measurement_temperature    169.98(10)
_cell_measurement_theta_max      28.1110
_cell_measurement_theta_min      1.8810
_cell_volume                     4641.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.12b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.12b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.12b (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_environment      N~2~
_diffrn_ambient_temperature      169.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      4.00  44.00   0.50   17.60    --   20.00  54.00 150.00   80
  2  \w    -71.00 -45.00   0.50   17.60    --   20.00  54.00 -60.00   52
  3  \w    -34.00  35.00   0.50   17.60    --   20.00  54.00 -60.00  138
  4  \w    -74.00 107.00   0.50   17.60    --   20.00  54.00  60.00  362
  5  \w    -13.00  12.00   0.50   17.60    --   20.00  54.00 -30.00   50
  6  \w    -71.00 -44.00   0.50   17.60    --   20.00  54.00   0.00   54
  7  \w     11.00  36.00   0.50   17.60    --   20.00  54.00   0.00   50
  8  \w    -70.00 -45.00   0.50   17.60    --   20.00  54.00 150.00   50
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0022644000
_diffrn_orient_matrix_UB_12      0.0266045000
_diffrn_orient_matrix_UB_13      0.0177809000
_diffrn_orient_matrix_UB_21      -0.0138286000
_diffrn_orient_matrix_UB_22      -0.0425908000
_diffrn_orient_matrix_UB_23      0.0106365000
_diffrn_orient_matrix_UB_31      0.0711323000
_diffrn_orient_matrix_UB_32      -0.0075092000
_diffrn_orient_matrix_UB_33      0.0026225000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            29170
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.100
_diffrn_reflns_theta_min         1.887
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.675
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87899
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.12b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       plank
_exptl_crystal_F_000             1924
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.197
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.55(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         10201
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0323P)^2^+5.8704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                9167
_reflns_number_total             10201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           14
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_original_formula_sum        'C47.95 H75.95 Br0.15 F O1.70 P2 Pd S0.85'
_cod_database_code               4134146
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd S O2 F1 C49 H77'
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.774
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.45(3)
 0.55(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Others
 Fixed Sof: C49(0.85) H49A(0.85) H49B(0.85) H49C(0.85) C46(0.85) C45(0.85)
 H45(0.85) C44(0.85) H44(0.85) C43(0.85) C48(0.85) H48(0.85) C47(0.85)
 H47(0.85) S1(0.85) O1(0.85) O2(0.85) Br1(0.15)
4.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C31(H31), C19(H19), C13(H13), C25(H25)
4.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B), C32(H32A,H32B), C11(H11A,H11B), C36(H36A,H36B),
 C10(H10A,H10B), C21(H21A,H21B), C30(H30A,H30B), C6(H6A,H6B), C24(H24A,H24B),
 C2(H2A,H2B), C5(H5A,H5B), C35(H35A,H35B), C26(H26A,H26B), C3(H3A,H3B),
 C14(H14A,H14B), C12(H12A,H12B), C34(H34A,H34B), C23(H23A,H23B), C28(H28A,H28B),
  C27(H27A,H27B), C33(H33A,H33B), C20(H20A,H20B), C22(H22A,H22B), C29(H29A,
 H29B), C17(H17A,H17B), C18(H18A,H18B), C4(H4A,H4B), C16(H16A,H16B), C15(H15A,
 H15B)
4.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C38(H38), C42(H42), C41(H41), C45(H45), C44(H44), C48(H48), C47(H47)
4.d Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C)
;
_shelx_res_checksum              71966
_shelx_hkl_checksum              28064
_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 1.106
_oxdiff_exptl_absorpt_empirical_full_min 0.910