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_4134142
_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 H82 F8 O4 P2 Pd2 S2'
_chemical_formula_sum            'C62 H82 F8 O4 P2 Pd2 S2'
_chemical_formula_weight         1382.13
_chemical_name_common            '[(4-F-C6H4)Pd(PCy3)(SO2C6H4CF3)]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
_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                 100.444(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.5764(10)
_cell_length_b                   24.600(2)
_cell_length_c                   9.5037(6)
_cell_measurement_reflns_used    8418
_cell_measurement_temperature    150.00(19)
_cell_measurement_theta_max      75.3090
_cell_measurement_theta_min      3.7270
_cell_volume                     3121.5(4)
_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(19)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_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    -44.00   9.00   1.00   12.50    --  -42.53  38.00 -30.00   53
  2  \w    -52.00 -26.00   1.00   12.50    --  -42.53 -57.00   0.00   26
  3  \w     14.00  39.00   1.00   12.50    --   42.53  77.00   0.00   25
  4  \w    -69.00  28.00   1.00   12.50    --  -42.53  57.00 150.00   97
  5  \w   -110.00 -66.00   1.00   12.50    --  -42.53 -57.00   0.00   44
  6  \w     88.00 118.00   1.00   60.00    --  111.00  30.00  60.00   30
  7  \w    139.00 171.00   1.00   60.00    --  111.00  30.00  60.00   32
  8  \w    135.00 161.00   1.00   60.00    --  111.00  45.00   0.00   26
  9  \w    143.00 172.00   1.00   60.00    --  111.00 125.00 -30.00   29
 10  \w    103.00 154.00   1.00   60.00    --  111.00 125.00 120.00   51
 11  \w     87.00 114.00   1.00   60.00    --  111.00  45.00   0.00   27
 12  \w     56.00  84.00   1.00   60.00    --  111.00 -30.00-120.00   28
 13  \w     54.00  80.00   1.00   60.00    --  111.00 -45.00-180.00   26
 14  \w     81.00 141.00   1.00   60.00    --  111.00 -77.00 -90.00   60
 15  \w     49.00  98.00   1.00   60.00    --  111.00 -45.00 -30.00   49
 16  \w     40.00  71.00   1.00   60.00    --  111.00 -30.00   0.00   31
 17  \w     42.00  67.00   1.00   60.00    --  111.00 -45.00 -60.00   25
 18  \w     31.00  60.00   1.00   60.00    --  111.00 -95.00 -90.00   29
 19  \w     48.00 120.00   1.00   60.00    --  111.00-125.00 -30.00   72
 20  \w     41.00  78.00   1.00   60.00    --  111.00 -45.00 120.00   37
 21  \w     44.00  91.00   1.00   60.00    --  111.00 -30.00 150.00   47
 22  \w     40.00  97.00   1.00   60.00    --  111.00 -45.00  60.00   57
;
_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      0.0469621000
_diffrn_orient_matrix_UB_12      0.0562060000
_diffrn_orient_matrix_UB_13      -0.0137118000
_diffrn_orient_matrix_UB_21      0.0697074000
_diffrn_orient_matrix_UB_22      -0.0089599000
_diffrn_orient_matrix_UB_23      0.1453912000
_diffrn_orient_matrix_UB_31      0.0790825000
_diffrn_orient_matrix_UB_32      -0.0263062000
_diffrn_orient_matrix_UB_33      -0.0762072000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            17104
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.409
_diffrn_reflns_theta_min         3.593
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.338
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61170
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_description       plank
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.277
_refine_diff_density_min         -1.117
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     406
_refine_ls_number_reflns         6435
_refine_ls_number_restraints     323
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0455P)^2^+10.6740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1464
_refine_ls_wR_factor_ref         0.1502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5746
_reflns_number_total             6435
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           11-CF3
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134142
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 S1 O2 P1 F4 C31 H41'
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.364
_reflns_odcompleteness_completeness 99.53
_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. Restrained distances
 F4A-C31A \\sim F3A-C31A \\sim F2A-C31A
 with sigma of 0.02
 C31A-C22 \\sim C31-C28
 with sigma of 0.02
 F1A-C28 \\sim F1-C22
 with sigma of 0.02
 C31-C29 \\sim C31-C27
 with sigma of 0.02
 F1A-C29 \\sim F1A-C27
 with sigma of 0.02
3. Restrained planarity
 F1A, C28, C27, C26, C25, C30, C29
 with sigma of 0.1
 C31, C28, C27, C26, C25, C30, C29
 with sigma of 0.1
 C19, C24, C23, C22, C21, C20, F1
 with sigma of 0.1
 C19, C24, C23, C22, C21, C20, C31A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C19 \\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim C20 \\sim F1: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C19 \\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim C20 \\sim C31A \\sim F2A
\\sim F3A \\sim F4A: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C25 \\sim C30 \\sim C29 \\sim C28 \\sim C27 \\sim C26 \\sim C31 \\sim F2 \\sim
F3 \\sim F4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C25 \\sim C30 \\sim C29 \\sim C28 \\sim C27 \\sim C26 \\sim F1A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C19, C24, C23, C22, C21, C20, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C24, C23, C22, C21, C20, C31A, F2A, F3A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C30, C29, C28, C27, C26, C31, F2, F3, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C30, C29, C28, C27, C26, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: F1(0.77) F3(0.77) F2(0.77) C31(0.77) F4(0.77) F2A(0.23) F4A(0.23)
 F3A(0.23) C31A(0.23) F1A(0.23)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C13(H13)
7.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C2(H2A,H2B), C8(H8A,H8B), C16(H16A,H16B), C14(H14A,H14B),
 C9(H9A,H9B), C15(H15A,H15B), C6(H6A,H6B), C17(H17A,H17B), C12(H12A,H12B),
 C10(H10A,H10B), C4(H4A,H4B), C5(H5A,H5B), C11(H11A,H11B), C3(H3A,H3B)
7.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C20(H20), C23(H23), C26(H26), C21(H21), C30(H30), C27(H27), C29(H29)
;
_shelx_res_checksum              39465
_shelx_hkl_checksum              70859
_ins_header
;
TITL 263aim18 in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  13.576378  24.600109   9.503749  90.0000 100.4436  90.0000
ZERR    4.00   0.000964   0.002305   0.000624   0.0000   0.0066   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H O F P S Pd
UNIT 124.00 164.00 8.00 16.00 4.00 4.00 4.00
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 1.653
_oxdiff_exptl_absorpt_empirical_full_min 0.595