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_4134148
_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         'C30 H40 F4 N O2 P Pd S'
_chemical_formula_sum            'C30 H40 F4 N O2 P Pd S'
_chemical_formula_weight         692.06
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.5300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.58590(10)
_cell_length_b                   20.2148(2)
_cell_length_c                   28.1308(3)
_cell_measurement_reflns_used    17980
_cell_measurement_temperature    150.00(13)
_cell_measurement_theta_max      76.1670
_cell_measurement_theta_min      3.8090
_cell_volume                     5991.75(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_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      150.00(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_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     -1.00  25.00   1.00    1.00    --  -42.66  38.00 -60.00   26
  2  \w    -47.00  30.00   1.00    1.00    --  -42.66  38.00  90.00   77
  3  \w   -111.00 -25.00   1.00    1.00    --  -42.66 -38.00 120.00   86
  4  \w   -129.00 -92.00   1.00    1.00    --  -42.66-178.00 -30.00   37
  5  \w     41.00  84.00   1.00    2.00    --  111.00 -45.00 150.00   43
  6  \w     50.00 139.00   1.00    2.00    --  111.00 -61.00 120.00   89
  7  \w     87.00 174.00   1.00    2.00    --  111.00  45.00  90.00   87
  8  \w     87.00 148.00   1.00    2.00    --  111.00   0.00 -90.00   61
  9  \w     91.00 117.00   1.00    2.00    --  111.00  77.00 -90.00   26
 10  \w    142.00 174.00   1.00    2.00    --  111.00 125.00-120.00   32
 11  \w    149.00 175.00   1.00    2.00    --  111.00  77.00 -90.00   26
 12  \w     57.00  83.00   1.00    2.00    --  111.00 -30.00 -30.00   26
 13  \w     45.00  84.00   1.00    2.00    --  111.00 -30.00 -60.00   39
 14  \w     43.00  87.00   1.00    2.00    --  111.00 -30.00-120.00   44
 15  \w     78.00 104.00   1.00    2.00    --  111.00 -95.00-180.00   26
 16  \w     94.00 120.00   1.00    2.00    --  111.00-125.00-150.00   26
 17  \w     71.00 106.00   1.00    2.00    --  111.00 -95.00 -60.00   35
 18  \w     51.00 120.00   1.00    2.00    --  111.00-125.00 -60.00   69
 19  \w     56.00  92.00   1.00    2.00    --  111.00 -95.00  60.00   36
 20  \w     30.00  55.00   1.00    2.00    --  111.00 -95.00 -60.00   25
 21  \w     31.00  57.00   1.00    2.00    --  111.00 -95.00-180.00   26
 22  \w     24.00  77.00   1.00    2.00    --  111.00   0.00 -90.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1251689000
_diffrn_orient_matrix_UB_12      0.0069223000
_diffrn_orient_matrix_UB_13      -0.0233298000
_diffrn_orient_matrix_UB_21      0.0747293000
_diffrn_orient_matrix_UB_22      0.0004679000
_diffrn_orient_matrix_UB_23      0.0497744000
_diffrn_orient_matrix_UB_31      0.0117944000
_diffrn_orient_matrix_UB_32      -0.0758967000
_diffrn_orient_matrix_UB_33      -0.0018493000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0332
_diffrn_reflns_av_unetI/netI     0.0328
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       -25
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            37849
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.166
_diffrn_reflns_theta_min         3.841
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.615
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76848
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
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    1.534
_exptl_crystal_description       prism
_exptl_crystal_F_000             2848
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.729
_refine_diff_density_min         -0.972
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     721
_refine_ls_number_reflns         12423
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0275
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0370P)^2^+0.1885P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0663
_refine_ls_wR_factor_ref         0.0687
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11267
_reflns_number_total             12423
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           20
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134148
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 F4 C30 P1 N S1 H40 O2'
_chemical_oxdiff_usercomment     C50H100N2BPMg
_shelx_estimated_absorpt_t_max   0.504
_shelx_estimated_absorpt_t_min   0.278
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C37(H37), C43(H43), C13(H13), C31(H31), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C39(H39A,H39B), C40(H40A,H40B), C2(H2A,H2B), C32(H32A,H32B),
 C18(H18A,H18B), C42(H42A,H42B), C5(H5A,H5B), C38(H38A,H38B), C36(H36A,H36B),
 C17(H17A,H17B), C4(H4A,H4B), C48(H48A,H48B), C3(H3A,H3B), C41(H41A,H41B),
 C47(H47A,H47B), C15(H15A,H15B), C14(H14A,H14B), C33(H33A,H33B), C8(H8A,H8B),
 C10(H10A,H10B), C12(H12A,H12B), C45(H45A,H45B), C46(H46A,H46B), C44(H44A,H44B),
  C9(H9A,H9B), C11(H11A,H11B), C34(H34A,H34B), C16(H16A,H16B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C57(H57), C27(H27), C55(H55), C58(H58), C25(H25), C54(H54), C24(H24),
 C50(H50), C20(H20), C28(H28), C51(H51), C53(H53), C21(H21), C23(H23)
;
_shelx_res_checksum              19424
_shelx_hkl_checksum              15526
_ins_header
;
TITL 264aim18 in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  10.585935  20.214833  28.130830  90.0000  95.5300  90.0000
ZERR    8.00   0.000117   0.000189   0.000271   0.0000   0.0010   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O F P S Pd
UNIT 240.00 320.00 8.00 16.00 32.00 8.00 8.00 8.00
TREF
HKLF 4
END
;
_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 1.307
_oxdiff_exptl_absorpt_empirical_full_min 0.827