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_4134141
_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         'C62 H88 F2 O4 P2 Pd2 S2'
_chemical_formula_sum            'C62 H88 F2 O4 P2 Pd2 S2'
_chemical_formula_weight         1274.18
_chemical_name_common            '[(4-F-C6H4)Pd(PCy3)(SO2C6H4Me)]2'
_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
_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                 99.501(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.3684(4)
_cell_length_b                   24.2919(6)
_cell_length_c                   9.5064(2)
_cell_measurement_reflns_used    16816
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      28.6390
_cell_measurement_theta_min      1.7520
_cell_volume                     3044.80(14)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_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     35.00  63.00   0.50   27.12    --   20.00  54.00 126.52   56
  2  \w     74.00 100.00   0.50   27.12    --   20.00  54.00 126.52   52
  3  \w    -51.00 -17.00   0.50   27.12    --   20.00  54.00  90.00   68
  4  \w     47.00  73.00   0.50   27.12    --   20.00  54.00  90.00   52
  5  \w    -71.00  22.00   0.50   27.12    --   20.00  54.00   0.00  186
  6  \w     35.00  71.00   0.50   27.12    --   20.00  54.00   0.00   72
  7  \w     76.00 109.00   0.50   27.12    --   20.00  54.00   0.00   66
  8  \w    -67.00 -41.00   0.50   27.12    --   20.00  54.00-120.00   52
  9  \w    -39.00  25.00   0.50   27.12    --   20.00  54.00-120.00  128
 10  \w    -73.00 -30.00   0.50   27.12    --   20.00  54.00 -60.00   86
 11  \w    -25.00  34.00   0.50   27.12    --   20.00  54.00 -60.00  118
 12  \w     60.00  86.00   0.50   27.12    --   20.00  54.00 -60.00   52
 13  \w    -71.00   5.00   0.50   27.12    --   20.00  54.00  60.00  152
 14  \w     13.00  63.00   0.50   27.12    --   20.00  54.00  60.00  100
 15  \w    -72.00 108.00   0.50   27.12    --   20.00  54.00 -90.00  360
 16  \w    -74.00  33.00   0.50   27.12    --   20.00  54.00-180.00  214
 17  \w    -70.00 -42.00   0.50   27.12    --   20.00  54.00 -10.27   56
 18  \w    -71.00 109.00   0.50   27.12    --   20.00  54.00 150.00  360
 19  \w    -68.00  99.00   0.50   27.12    --   20.00  54.00-150.00  334
 20  \w    -73.00 -46.00   0.50   27.12    --   20.00  54.00 126.52   54
;
_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      0.0197261000
_diffrn_orient_matrix_UB_12      -0.0002273000
_diffrn_orient_matrix_UB_13      0.0740115000
_diffrn_orient_matrix_UB_21      0.0025252000
_diffrn_orient_matrix_UB_22      0.0291673000
_diffrn_orient_matrix_UB_23      -0.0000676000
_diffrn_orient_matrix_UB_31      -0.0499864000
_diffrn_orient_matrix_UB_32      0.0012705000
_diffrn_orient_matrix_UB_33      0.0157231000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            59366
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         1.757
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.762
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89250
_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    1.390
_exptl_crystal_description       plank
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.825
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         6673
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0198P)^2^+3.5024P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0802
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5651
_reflns_number_total             6673
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           11
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134141
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd2 P2 F2 C62 H88 O4'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.702
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C7(H7), C13(H13), C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C17(H17A,H17B), C8(H8A,H8B), C12(H12A,H12B), C11(H11A,H11B),
 C14(H14A,H14B), C3(H3A,H3B), C2(H2A,H2B), C6(H6A,H6B), C16(H16A,H16B),
 C15(H15A,H15B), C9(H9A,H9B), C10(H10A,H10B), C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C20(H20), C26(H26), C30(H30), C21(H21), C23(H23), C27(H27), C29(H29)
2.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              13464
_shelx_hkl_checksum              99739
_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 1.115
_oxdiff_exptl_absorpt_empirical_full_min 0.869