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_4134139
_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         'C45 H76 O4 P2 Pd S'
_chemical_formula_sum            'C45 H76 O4 P2 Pd S'
_chemical_formula_weight         881.45
_chemical_name_common            Pd(PCy3)2(OAc)(SO2C6H4Me)
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                87.089(2)
_cell_angle_beta                 73.891(2)
_cell_angle_gamma                76.606(2)
_cell_formula_units_Z            2
_cell_length_a                   10.2937(3)
_cell_length_b                   13.7632(3)
_cell_length_c                   17.3117(4)
_cell_measurement_reflns_used    29929
_cell_measurement_temperature    169.97(18)
_cell_measurement_theta_max      30.5240
_cell_measurement_theta_min      1.9050
_cell_volume                     2291.99(10)
_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      169.97(18)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.990
_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    -74.00 110.00   0.50   17.91    --   20.00  54.00  32.17  368
  2  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00 -87.21  368
  3  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00 150.00  368
  4  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00  90.00  368
  5  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00   0.00  368
  6  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00-140.23  368
  7  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00 -60.00  368
  8  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00  49.51  368
  9  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00  49.51  368
 10  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00 -30.00  368
 11  \w    -74.00 105.50   0.50   17.91    --   20.00  54.00 115.38  359
 12  \w    -74.00 110.00   0.50   17.91    --   20.00  54.00 176.85  368
;
_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      -0.0116272000
_diffrn_orient_matrix_UB_12      0.0385274000
_diffrn_orient_matrix_UB_13      -0.0277656000
_diffrn_orient_matrix_UB_21      0.0265173000
_diffrn_orient_matrix_UB_22      -0.0355886000
_diffrn_orient_matrix_UB_23      -0.0320116000
_diffrn_orient_matrix_UB_31      -0.0677138000
_diffrn_orient_matrix_UB_32      -0.0074946000
_diffrn_orient_matrix_UB_33      0.0049298000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            77121
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         1.939
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.559
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63532
_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    1.277
_exptl_crystal_description       plank
_exptl_crystal_F_000             940
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.797
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         10025
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0259
_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^)+(0.0249P)^2^+1.6068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0622
_refine_ls_wR_factor_ref         0.0642
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9136
_reflns_number_total             10025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134139
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd S O4 P2 C45 H76'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.730
_reflns_odcompleteness_completeness 99.24
_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), C25(H25), C1(H1), C19(H19), C13(H13), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C8(H8A,H8B), C23(H23A,H23B), C26(H26A,H26B), C32(H32A,H32B),
 C20(H20A,H20B), C14(H14A,H14B), C30(H30A,H30B), C12(H12A,H12B), C36(H36A,H36B),
  C33(H33A,H33B), C22(H22A,H22B), C15(H15A,H15B), C9(H9A,H9B), C6(H6A,H6B),
 C18(H18A,H18B), C27(H27A,H27B), C34(H34A,H34B), C11(H11A,H11B), C28(H28A,H28B),
  C10(H10A,H10B), C2(H2A,H2B), C17(H17A,H17B), C21(H21A,H21B), C3(H3A,H3B),
 C35(H35A,H35B), C29(H29A,H29B), C5(H5A,H5B), C16(H16A,H16B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C42(H42), C38(H38), C41(H41), C39(H39)
2.d Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              57891
_shelx_hkl_checksum              2968
_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 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.750