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_4134147
_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 H88 F2 O6 P2 Pd2 S2'
_chemical_formula_sum            'C62 H88 F2 O6 P2 Pd2 S2'
_chemical_formula_weight         1306.18
_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             2019-11-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                62.876(5)
_cell_angle_beta                 78.221(5)
_cell_angle_gamma                78.401(4)
_cell_formula_units_Z            1
_cell_length_a                   9.5185(6)
_cell_length_b                   13.3787(6)
_cell_length_c                   14.2586(8)
_cell_measurement_reflns_used    6201
_cell_measurement_temperature    150.01(11)
_cell_measurement_theta_max      75.9900
_cell_measurement_theta_min      4.7410
_cell_volume                     1569.84(17)
_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      150.01(11)
_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 0.987
_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    -50.00  -4.00   1.00    3.00    --  -42.66  38.00-120.00   46
  2  \w   -100.00 -27.00   1.00    3.00    --  -42.66 -38.00-150.00   73
  3  \w   -106.00 -18.00   1.00    3.00    --  -42.66 -57.00 -60.00   88
  4  \w    -67.00  12.00   1.00    3.00    --  -42.66  57.00  90.00   79
  5  \w   -113.00 -75.00   1.00    3.00    --  -42.66-140.00   9.00   38
  6  \w   -127.00 -84.00   1.00    3.00    --  -42.66 178.00  90.00   43
  7  \w     50.00  76.00   1.00   12.00    --  111.00 -45.00 -60.00   26
  8  \w     61.00  98.00   1.00   12.00    --  111.00 -45.00-120.00   37
  9  \w     56.00  99.00   1.00   12.00    --  111.00 -95.00 -90.00   43
 10  \w     85.00 110.00   1.00   12.00    --  111.00-125.00-120.00   25
 11  \w     96.00 121.00   1.00   12.00    --  111.00-125.00 -90.00   25
 12  \w     80.00 117.00   1.00   12.00    --  111.00-125.00   0.00   37
 13  \w    111.00 141.00   1.00   12.00    --  111.00 -77.00  60.00   30
 14  \w     71.00 108.00   1.00   12.00    --  111.00 -95.00 120.00   37
 15  \w     63.00 121.00   1.00   12.00    --  111.00-125.00  90.00   58
 16  \w     64.00  90.00   1.00   12.00    --  111.00 -45.00  90.00   26
 17  \w     63.00 135.00   1.00   12.00    --  111.00 -61.00 150.00   72
 18  \w    143.00 178.00   1.00   12.00    --  111.00  45.00  30.00   35
 19  \w     92.00 127.00   1.00   12.00    --  111.00  45.00  30.00   35
 20  \w     47.00  74.00   1.00   12.00    --  111.00 -30.00 150.00   27
 21  \w     37.00  79.00   1.00   12.00    --  111.00 -30.00 120.00   42
 22  \w     46.00  89.00   1.00   12.00    --  111.00 -45.00  60.00   43
 23  \w     37.00  91.00   1.00   12.00    --  111.00 -30.00  60.00   54
 24  \w     41.00  91.00   1.00   12.00    --  111.00 -77.00  60.00   50
 25  \w     37.00  91.00   1.00   12.00    --  111.00 -30.00   0.00   54
 26  \w     45.00  71.00   1.00   12.00    --  111.00 -95.00 -60.00   26
 27  \w     30.00  91.00   1.00   12.00    --  111.00 -95.00   0.00   61
 28  \w     33.00  75.00   1.00   12.00    --  111.00 -95.00  30.00   42
 29  \w     39.00  85.00   1.00   12.00    --  111.00 -30.00-150.00   46
 30  \w     24.00 173.00   1.00   12.00    --  111.00   0.00-150.00  149
 31  \w    121.00 152.00   1.00   12.00    --  111.00  77.00-150.00   31
 32  \w     86.00 111.00   1.00   12.00    --  111.00  77.00-150.00   25
;
_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      0.1201008000
_diffrn_orient_matrix_UB_12      0.0217307000
_diffrn_orient_matrix_UB_13      -0.0951682000
_diffrn_orient_matrix_UB_21      -0.1150225000
_diffrn_orient_matrix_UB_22      0.0564618000
_diffrn_orient_matrix_UB_23      -0.0768808000
_diffrn_orient_matrix_UB_31      0.0103179000
_diffrn_orient_matrix_UB_32      0.1154984000
_diffrn_orient_matrix_UB_33      -0.0042981000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0680
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            15016
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.836
_diffrn_reflns_theta_min         3.741
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.150
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89917
_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    1.382
_exptl_crystal_description       plate
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.961
_refine_diff_density_min         -1.198
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     499
_refine_ls_number_reflns         15016
_refine_ls_number_restraints     604
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0685
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1313P)^2^+2.4994P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.2221
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12184
_reflns_number_total             15016
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           17
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134147
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 P1 O3 S1 F1 C31 H44'
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.526
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.840(2)
 0.160(2)
2. 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
3. Restrained distances
 O3-C31 = O3A-C31A
 1.45 with sigma of 0.01
 C30A-C25A \\sim C25A-C26A \\sim C26A-C27A \\sim C27A-C28A \\sim C28A-C29A
\\sim C29A-C30A
 with sigma of 0.02
 C30A-C28A \\sim C30A-C28A \\sim C27A-C25A \\sim C27A-C29A \\sim C29A-C25A
\\sim C28A-C26A
 with sigma of 0.04
 C25-C26 \\sim C26-C27 \\sim C27-C28 \\sim C28-C29 \\sim C29-C30 \\sim C30-C25
 with sigma of 0.02
 C25-C29 \\sim C25-C29 \\sim C28-C26 \\sim C28-C30 \\sim C30-C26 \\sim C29-C27
 with sigma of 0.04
 C24A-C23A \\sim C23A-C22A \\sim C22A-C21A \\sim C21A-C20A \\sim C20A-C19A
\\sim C19A-C24A
 with sigma of 0.02
 C24A-C20A \\sim C24A-C20A \\sim C21A-C23A \\sim C21A-C19A \\sim C19A-C23A
\\sim C20A-C22A
 with sigma of 0.04
 C24-C23 \\sim C23-C22 \\sim C22-C21 \\sim C21-C20 \\sim C20-C19 \\sim C19-C24
 with sigma of 0.02
 C24-C20 \\sim C24-C20 \\sim C21-C23 \\sim C21-C19 \\sim C19-C23 \\sim C20-C22
 with sigma of 0.04
 S1-O2 \\sim S1-O2A
 with sigma of 0.02
 Pd1-O1A \\sim Pd1-O1
 with sigma of 0.02
 S1-O1A \\sim S1-O1
 with sigma of 0.02
 O3A-C31A \\sim O3-C31
 with sigma of 0.02
4. Restrained planarity
 C24A, C23A, C22A, C21A, C20A, C19A, F1A
 with sigma of 0.1
 C24, C23, C22, C21, C20, C19, F1
 with sigma of 0.1
 C30A, C25A, C26A, C27A, C28A, C29A, O3A
 with sigma of 0.1
 C25, C26, C27, C28, C29, C30, O3
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Pd1 \\sim O1 \\sim S1 \\sim O2 \\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim
C20 \\sim C19 \\sim F1 \\sim O3 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C30 \\sim C31: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Pd1 \\sim O1A \\sim S1 \\sim O2A \\sim C24A \\sim C23A \\sim C22A \\sim C21A
\\sim C20A \\sim C19A \\sim F1A \\sim O3A \\sim C25A \\sim C26A \\sim C27A
\\sim C28A \\sim C29A \\sim C30A \\sim C31A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
6. Rigid body (RIGU) restrains
 Pd1, O1, S1, O2, C24, C23, C22, C21, C20, C19, F1, O3, C25, C26, C27, C28,
 C29, C30, C31
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Pd1, O1A, S1, O2A, C24A, C23A, C22A, C21A, C20A, C19A, F1A, O3A, C25A, C26A,
 C27A, C28A, C29A, C30A, C31A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(O1A)=Sof(F1A)=Sof(O3A)=Sof(C30A)=Sof(H30A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C24A)=Sof(H24A)=
 Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=
 Sof(C19A)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(O2A)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(O1)=Sof(O3)=Sof(C25)=Sof(C26)=
 Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=
 Sof(F1)=Sof(C24)=Sof(H24)=Sof(C23)=Sof(H23)=Sof(C22)=Sof(C21)=Sof(H21)=
 Sof(C20)=Sof(H20)=Sof(C19)=Sof(O2)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C13(H13)
8.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C14(H14A,H14B), C6(H6A,H6B), C5(H5A,H5B), C12(H12A,H12B),
 C3(H3A,H3B), C2(H2A,H2B), C8(H8A,H8B), C15(H15A,H15B), C4(H4A,H4B), C10(H10A,
 H10B), C9(H9A,H9B), C17(H17A,H17B), C18(H18A,H18B), C16(H16A,H16B)
8.c Me refined with riding coordinates:
 C31A(H31D,H31E,H31F)
8.d Aromatic/amide H refined with riding coordinates:
 C30A(H30A), C26A(H26A), C27A(H27A), C29A(H29A), C26(H26), C27(H27), C29(H29),
 C30(H30), C24A(H24A), C23A(H23A), C21A(H21A), C20A(H20A), C24(H24), C23(H23),
 C21(H21), C20(H20)
8.e Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              23491
_shelx_hkl_checksum              94753
_ins_header
;
TITL 249aim18 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184   9.518484  13.378724  14.258588  62.8763  78.2212  78.4006
ZERR    2.00   0.000557   0.000559   0.000819   0.0052   0.0049   0.0045
LATT  1
SFAC C H O F P S Pd
UNIT 62.00 88.00 6.00 2.00 2.00 2.00 2.00
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 1.163
_oxdiff_exptl_absorpt_empirical_full_min 0.857