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_4134140
_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         'C28 H41 N2 O4 P Pd S2, C H2 Cl2'
_chemical_formula_sum            'C29 H43 Cl2 N2 O4 P Pd S2'
_chemical_formula_weight         756.04
_chemical_name_common            Pd(PCy3)(SO2C5H3N)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             2019-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.295(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0029(2)
_cell_length_b                   29.0336(8)
_cell_length_c                   11.5546(3)
_cell_measurement_reflns_used    20710
_cell_measurement_temperature    169.98(10)
_cell_measurement_theta_max      30.4820
_cell_measurement_theta_min      1.9060
_cell_volume                     3328.53(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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_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    -73.00 -47.00   0.50    7.44    --   20.00  54.00 150.00   52
  2  \w    -15.00  32.00   0.50    7.44    --   20.00  54.00 150.00   94
  3  \w     63.00  89.00   0.50    7.44    --   20.00  54.00 150.00   52
  4  \w    -68.00  57.00   0.50    7.44    --   20.00  54.00  30.00  250
  5  \w    -72.00  11.00   0.50    7.44    --   20.00  54.00  90.00  166
  6  \w     74.00 100.00   0.50    7.44    --   20.00  54.00  90.00   52
  7  \w    -74.00  89.00   0.50    7.44    --   20.00  54.00 -30.00  326
  8  \w    -72.00 -47.00   0.50    7.44    --   20.00  54.00-180.00   50
  9  \w    -26.00   1.00   0.50    7.44    --   20.00  54.00-180.00   54
 10  \w     55.00 107.00   0.50    7.44    --   20.00  54.00-180.00  104
 11  \w    -74.00  22.00   0.50    7.44    --   20.00  54.00-120.00  192
 12  \w     44.00  70.00   0.50    7.44    --   20.00  54.00-120.00   52
 13  \w    -65.00  71.00   0.50    7.44    --   20.00  54.00  60.00  272
 14  \w    -73.00 -46.00   0.50    7.44    --   20.00  54.00 -60.00   54
 15  \w     54.00  82.00   0.50    7.44    --   20.00  54.00 -60.00   56
 16  \w    -74.00 -49.00   0.50    7.44    --   20.00  54.00-150.00   50
 17  \w     31.00  56.00   0.50    7.44    --   20.00  54.00-150.00   50
 18  \w    -63.00 -37.00   0.50    7.44    --   20.00  54.00   0.00   52
 19  \w     16.00  42.00   0.50    7.44    --   20.00  54.00   0.00   52
 20  \w    -66.00  56.00   0.50    7.44    --   20.00  54.00 120.00  244
 21  \w     22.00  49.00   0.50    7.44    --   20.00  54.00 -90.00   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      0.0297990000
_diffrn_orient_matrix_UB_12      -0.0012688000
_diffrn_orient_matrix_UB_13      0.0589720000
_diffrn_orient_matrix_UB_21      -0.0040907000
_diffrn_orient_matrix_UB_22      -0.0243851000
_diffrn_orient_matrix_UB_23      -0.0023626000
_diffrn_orient_matrix_UB_31      0.0648364000
_diffrn_orient_matrix_UB_32      -0.0009182000
_diffrn_orient_matrix_UB_33      -0.0186143000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            57892
_diffrn_reflns_point_group_measured_fraction_full 0.996
_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         1.910
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.928
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82074
_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    1.509
_exptl_crystal_description       plate
_exptl_crystal_F_000             1560
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.368
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     398
_refine_ls_number_reflns         7301
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0252
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0187P)^2^+2.8918P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0535
_refine_ls_wR_factor_ref         0.0559
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6341
_reflns_number_total             7301
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           10
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134140
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 S1 O4 P1 N1 C25 H40'
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.708
_reflns_odcompleteness_completeness 99.33
_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
2. Restrained distances
 Cl2-C29 = Cl1-C29
 1.771 with sigma of 0.01
 Cl2-Cl1
 2.916 with sigma of 0.03
 Cl1A-C29A = Cl2A-C29A
 1.771 with sigma of 0.01
 Cl1A-Cl2A
 2.916 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim Cl1 \\sim C29: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Cl1A \\sim Cl2A \\sim C29A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
4. Rigid body (RIGU) restrains
 Cl2, Cl1, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1A, Cl2A, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(C29A)=Sof(H29C)=Sof(H29D)=1-FVAR(1)
 Sof(Cl2)=Sof(Cl1)=Sof(C29)=Sof(H29A)=Sof(H29B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C13(H13), C1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C3(H3A,H3B),
 C10(H10A,H10B), C17(H17A,H17B), C14(H14A,H14B), C2(H2A,H2B), C6(H6A,H6B),
 C4(H4A,H4B), C18(H18A,H18B), C16(H16A,H16B), C15(H15A,H15B), C5(H5A,H5B),
 C29(H29A,H29B), C29A(H29C,H29D)
6.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C22(H22), C20(H20), C21(H21), C25(H25), C28(H28), C26(H26), C27(H27)
;
_shelx_res_checksum              72192
_shelx_hkl_checksum              48420
_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 1.227
_oxdiff_exptl_absorpt_empirical_full_min 0.887