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_4134144
_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 H43 F N O3 P Pd S, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C30.5 H44 Cl F N O3 P Pd S'
_chemical_formula_weight         696.54
_chemical_name_common            (4-F-C6H4)Pd(PCy3)(SO2C6H3NOMe)
_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 1.3-alpha
(compiled 2019.10.31 svn.r3677 for OlexSys, GUI svn.r5972)
;
_cell_angle_alpha                79.425(3)
_cell_angle_beta                 82.298(3)
_cell_angle_gamma                78.361(2)
_cell_formula_units_Z            2
_cell_length_a                   8.8944(3)
_cell_length_b                   10.3439(3)
_cell_length_c                   17.8359(7)
_cell_measurement_reflns_used    8352
_cell_measurement_temperature    150.01(12)
_cell_measurement_theta_max      76.2100
_cell_measurement_theta_min      4.3790
_cell_volume                     1571.88(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(12)
_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 0.983
_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    -13.00  13.00   1.00    1.45    --  -42.66  38.00 -30.00   26
  2  \w    -49.00  29.00   1.00    1.45    --  -42.66  38.00  90.00   78
  3  \w    -50.00  28.00   1.00    1.45    --  -42.66  38.00 -60.00   78
  4  \w   -113.00 -19.00   1.00    1.45    --  -42.66 -57.00 150.00   94
  5  \w     98.00 125.00   1.00    1.45    --   42.66-178.00 -90.00   27
  6  \w     61.00  96.00   1.00    1.45    --   42.66-178.00 -90.00   35
  7  \w   -128.00 -43.00   1.00    1.45    --  -42.66 178.00-120.00   85
  8  \w     88.00 136.00   1.00    5.79    --  111.00 -77.00-150.00   48
  9  \w    101.00 155.00   1.00    5.79    --  111.00 -15.00 -60.00   54
 10  \w    105.00 159.00   1.00    5.79    --  111.00  45.00  30.00   54
 11  \w     99.00 151.00   1.00    5.79    --  111.00 -15.00  60.00   52
 12  \w     96.00 121.00   1.00    5.79    --  111.00-125.00 120.00   25
 13  \w     94.00 121.00   1.00    5.79    --  111.00-125.00   0.00   27
 14  \w     62.00 107.00   1.00    5.79    --  111.00 -95.00-120.00   45
 15  \w     72.00 121.00   1.00    5.79    --  111.00-125.00-150.00   49
 16  \w     67.00  94.00   1.00    5.79    --  111.00 -45.00-150.00   27
 17  \w     67.00  94.00   1.00    5.79    --  111.00 -45.00-180.00   27
 18  \w     45.00  75.00   1.00    5.79    --  111.00 -45.00 -90.00   30
 19  \w     45.00  72.00   1.00    5.79    --  111.00 -15.00 -60.00   27
 20  \w     41.00  97.00   1.00    5.79    --  111.00 -45.00   0.00   56
 21  \w     71.00  96.00   1.00    5.79    --  111.00 -45.00  60.00   25
 22  \w     44.00  94.00   1.00    5.79    --  111.00 -15.00  60.00   50
 23  \w     41.00 141.00   1.00    5.79    --  111.00 -77.00   0.00  100
 24  \w     51.00  82.00   1.00    5.79    --  111.00-125.00 120.00   31
 25  \w     39.00 107.00   1.00    5.79    --  111.00 -95.00   0.00   68
 26  \w     44.00  81.00   1.00    5.79    --  111.00 -45.00 120.00   37
 27  \w     38.00  69.00   1.00    5.79    --  111.00 -30.00  60.00   31
 28  \w     37.00  63.00   1.00    5.79    --  111.00 -77.00-150.00   26
 29  \w     38.00  94.00   1.00    5.79    --  111.00 -95.00-150.00   56
 30  \w     42.00  68.00   1.00    5.79    --  111.00 -30.00-180.00   26
 31  \w     34.00 140.00   1.00    5.79    --  111.00 -15.00-150.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0641642000
_diffrn_orient_matrix_UB_12      0.0420090000
_diffrn_orient_matrix_UB_13      0.0782882000
_diffrn_orient_matrix_UB_21      -0.1613004000
_diffrn_orient_matrix_UB_22      -0.0205947000
_diffrn_orient_matrix_UB_23      -0.0120931000
_diffrn_orient_matrix_UB_31      0.0381925000
_diffrn_orient_matrix_UB_32      -0.1468021000
_diffrn_orient_matrix_UB_33      0.0390441000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            14931
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.141
_diffrn_reflns_theta_min         4.422
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.953
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88286
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (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    1.472
_exptl_crystal_description       plank
_exptl_crystal_F_000             722
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.787
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         6464
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0292
_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^)+(0.0392P)^2^+0.0455P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0703
_refine_ls_wR_factor_ref         0.0734
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5859
_reflns_number_total             6464
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           12-OMe
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_original_formula_sum        'C30.50 H44 Cl F N O3 P Pd S'
_cod_database_code               4134144
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd P F N C30.5 S O3 H44 Cl'
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.443
_reflns_odcompleteness_completeness 99.63
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C31 = Cl3-C31
 1.771 with sigma of 0.01
 Cl2-Cl3
 2.916 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim Cl3 \\sim C31: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 Cl2, Cl3, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl2(0.5) Cl3(0.5) C31(0.5) H31A(0.5) H31B(0.5)
6.a Ternary CH refined with riding coordinates:
 C13(H13), C7(H7), C1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C3(H3A,H3B), C14(H14A,H14B), C17(H17A,H17B), C2(H2A,H2B),
 C4(H4A,H4B), C5(H5A,H5B), C15(H15A,H15B), C6(H6A,H6B), C16(H16A,H16B),
 C12(H12A,H12B), C8(H8A,H8B), C11(H11A,H11B), C10(H10A,H10B), C9(H9A,H9B),
 C31(H31A,H31B)
6.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C29(H29), C26(H26), C20(H20), C24(H24), C23(H23), C21(H21)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C)
;
_shelx_res_checksum              33497
_shelx_hkl_checksum              14593
_ins_header
;
TITL 246aim18 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184   8.894440  10.343879  17.835880  79.4248  82.2978  78.3609
ZERR    2.00   0.000292   0.000262   0.000724   0.0028   0.0030   0.0025
LATT  1
SFAC C H N O F P S Cl Pd
UNIT 61.00 88.00 2.00 6.00 2.00 2.00 2.00 2.00 2.00
TREF
HKLF 4
END
;
_olex2_date_sample_data_collection 2018-06-03
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.815