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_4134143
_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         'C29 H41 F N O2 P Pd S, C3 H7'
_chemical_formula_sum            'C32 H48 F N O2 P Pd S'
_chemical_formula_weight         667.14
_chemical_name_common            (4-F-C6H4)Pd(PCy3)(SO2C6H4N)
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/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                 130.842(11)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.707(2)
_cell_length_b                   9.0995(3)
_cell_length_c                   27.7743(18)
_cell_measurement_reflns_used    14888
_cell_measurement_temperature    169.98(10)
_cell_measurement_theta_max      29.2210
_cell_measurement_theta_min      1.9280
_cell_volume                     6444.6(12)
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   14.93    --   20.00  54.00 -39.69  368
  2  \w    -74.00 110.00   0.50   14.93    --   20.00  54.00-138.43  368
  3  \w    -74.00 110.00   0.50   14.93    --   20.00  54.00  89.68  368
  4  \w    -74.00 110.00   0.50   14.93    --   20.00  54.00-102.76  368
  5  \w    -74.00 110.00   0.50   14.93    --   20.00  54.00-180.00  368
  6  \w    -74.00 110.00   0.50   14.93    --   20.00  54.00-180.00  368
  7  \w    -22.00  90.00   0.50   14.93    --   20.00  54.00  60.00  224
  8  \w    -74.00  90.00   0.50   14.93    --   20.00  54.00 -77.28  328
  9  \w    -69.00  40.00   0.50   14.93    --   20.00  54.00   0.00  218
 10  \w    -73.00  97.00   0.50   14.93    --   20.00  54.00 120.00  340
 11  \w    -73.00 -26.00   0.50   14.93    --   20.00  54.00-116.79   94
 12  \w    -18.00   8.00   0.50   14.93    --   20.00  54.00-116.79   52
 13  \w    -62.00 -10.00   0.50   14.93    --   20.00  54.00 -30.00  104
 14  \w    -74.00  66.00   0.50   14.93    --   20.00  54.00-171.23  280
 15  \w    -64.00 -30.00   0.50   14.93    --   20.00  54.00  73.58   68
;
_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      0.0061243000
_diffrn_orient_matrix_UB_12      0.0175101000
_diffrn_orient_matrix_UB_13      0.0290957000
_diffrn_orient_matrix_UB_21      0.0251904000
_diffrn_orient_matrix_UB_22      0.0244523000
_diffrn_orient_matrix_UB_23      0.0127224000
_diffrn_orient_matrix_UB_31      -0.0100611000
_diffrn_orient_matrix_UB_32      0.0719783000
_diffrn_orient_matrix_UB_33      -0.0113559000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1018
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            92978
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         1.938
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.724
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55949
_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    1.375
_exptl_crystal_description       plank
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.803
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         7123
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0354P)^2^+10.9273P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0886
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5559
_reflns_number_total             7123
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           12
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_original_cell_volume        6444.7(10)
_cod_database_code               4134143
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd N F P S O2  C28 H41'
_chemical_oxdiff_usercomment     'NMR tube crystals'
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.670
_reflns_odcompleteness_completeness 99.94
_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,H,H,H) groups
2. Restrained distances
 C32-C31 = C31A-C32A = C31A-C30 = C31-C30
 1.5 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C30 \\sim C31 \\sim C32A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C30 \\sim C31A \\sim C32: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
4. Rigid body (RIGU) restrains
 C30, C31, C32A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30, C31A, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(C32A)=
 Sof(H32C)=Sof(H32D)=1-FVAR(1)
 Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C31)=Sof(H31C)=
 Sof(H31D)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C13(H13)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C2(H2A,H2B), C6(H6A,H6B), C12(H12A,H12B), C8(H8A,H8B), C5(H5A,
 H5B), C4(H4A,H4B), C3(H3A,H3B), C18(H18A,H18B), C15(H15A,H15B), C17(H17A,H17B),
  C11(H11A,H11B), C9(H9A,H9B), C16(H16A,H16B), C10(H10A,H10B), C32(H32A,H32B),
 C31A(H31A,H31B), C31(H31C,H31D), C32A(H32C,H32D)
6.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C20(H20), C24(H24), C27(H27), C23(H23), C21(H21), C25(H25), C26(H26)
6.d Idealised Me refined as rotating group:
 C30(H30D,H30E,H30F), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              61682
_shelx_hkl_checksum              186
_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 1.362
_oxdiff_exptl_absorpt_empirical_full_min 0.735