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_4134145
_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         'C66 H98 F2 N2 O4 P2 Pd2 S2, 2(C H Cl3)'
_chemical_formula_sum            'C68 H100 Cl6 F2 N2 O4 P2 Pd2 S2'
_chemical_formula_weight         1599.05
_chemical_name_common            (4-F-C6H4)Pd(PCy3)(SO2C6H3NtBu)
_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 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                64.568(5)
_cell_angle_beta                 86.354(5)
_cell_angle_gamma                77.968(5)
_cell_formula_units_Z            1
_cell_length_a                   12.1932(7)
_cell_length_b                   13.1620(7)
_cell_length_c                   13.4651(8)
_cell_measurement_reflns_used    5922
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      75.8540
_cell_measurement_theta_min      3.7150
_cell_volume                     1907.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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  90.00   1.00    2.00    --    0.00  57.00  30.00   40
  2  \w    -87.00 -37.00   1.00    2.00    --    0.00 178.00 120.00   50
  3  \w    -36.00  28.00   1.00    2.00    --    0.00  57.00  30.00   64
  4  \w    -42.00  29.00   1.00    4.00    --  -60.50  30.00   0.00   71
  5  \w   -141.00 -80.00   1.00    4.00    --  -60.50 -94.00 120.00   61
  6  \w   -138.00 -20.00   1.00    4.00    --  -60.50 -61.00  60.00  118
  7  \w    -83.00  -4.00   1.00    4.00    --  -60.50 125.00 -30.00   79
  8  \w    -30.00  86.00   1.00    4.00    --   60.50 -30.00  90.00  116
  9  \w     96.00 152.00   1.00    4.00    --   60.50 125.00  60.00   56
 10  \w    116.00 143.00   1.00    4.00    --   60.50 125.00 120.00   27
 11  \w    126.00 151.00   1.00    4.00    --   60.50 125.00-150.00   25
 12  \w    108.00 151.00   1.00    4.00    --   60.50 125.00   0.00   43
 13  \w     45.00 115.00   1.00    4.00    --   60.50-125.00-150.00   70
 14  \w     29.00 112.00   1.00    4.00    --  121.00-111.00 -60.00   83
 15  \w     67.00  94.00   1.00    4.00    --  121.00 178.00 -60.00   27
 16  \w    103.00 142.00   1.00    4.00    --  121.00 111.00 -60.00   39
 17  \w     33.00 103.00   1.00    4.00    --  121.00-111.00-180.00   70
 18  \w     87.00 112.00   1.00    4.00    --  121.00-111.00  30.00   25
 19  \w    152.00 177.00   1.00    4.00    --  121.00  63.00  60.00   25
 20  \w     78.00 142.00   1.00    4.00    --  121.00  63.00  90.00   64
 21  \w     31.00  72.00   1.00    4.00    --  121.00 -25.00-180.00   41
 22  \w    100.00 177.00   1.00    4.00    --  121.00 111.00  90.00   77
 23  \w     92.00 176.00   1.00    4.00    --  121.00  37.00   0.00   84
 24  \w    114.00 147.00   1.00    4.00    --  121.00  63.00  60.00   33
 25  \w     50.00  77.00   1.00    4.00    --  121.00-111.00  90.00   27
 26  \w     40.00  82.00   1.00    4.00    --  121.00 -37.00 -60.00   42
 27  \w     85.00 112.00   1.00    4.00    --  121.00-111.00 150.00   27
 28  \w     54.00 112.00   1.00    4.00    --  121.00-111.00-120.00   58
 29  \w    117.00 144.00   1.00    4.00    --  121.00 111.00-180.00   27
 30  \w     30.00  57.00   1.00    4.00    --  121.00-111.00 150.00   27
 31  \w    115.00 149.00   1.00    4.00    --  121.00 178.00  90.00   34
 32  \w     57.00  86.00   1.00    4.00    --  121.00 178.00  90.00   29
 33  \w     39.00  92.00   1.00    4.00    --  121.00 -25.00 -30.00   53
 34  \w     65.00 125.00   1.00    4.00    --  121.00 178.00  30.00   60
 35  \w    153.00 178.00   1.00    4.00    --  121.00 111.00 -60.00   25
 36  \w     46.00  91.00   1.00    4.00    --  121.00 -37.00 120.00   45
 37  \w     46.00 165.00   1.00    4.00    --  121.00 -77.00   0.00  119
 38  \w     86.00 111.00   1.00    4.00    --  121.00-111.00  90.00   25
 39  \w     43.00  90.00   1.00    4.00    --  121.00-111.00 -90.00   47
;
_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      0.0659312000
_diffrn_orient_matrix_UB_12      0.0342244000
_diffrn_orient_matrix_UB_13      0.0707385000
_diffrn_orient_matrix_UB_21      0.0546992000
_diffrn_orient_matrix_UB_22      -0.1271364000
_diffrn_orient_matrix_UB_23      0.0669724000
_diffrn_orient_matrix_UB_31      0.0967681000
_diffrn_orient_matrix_UB_32      0.0130308000
_diffrn_orient_matrix_UB_33      -0.0810844000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15361
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.511
_diffrn_reflns_theta_min         3.636
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.038
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (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    1.392
_exptl_crystal_description       prism
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.155
_refine_diff_density_min         -1.820
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     596
_refine_ls_number_reflns         7882
_refine_ls_number_restraints     504
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0678P)^2^+1.9120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1324
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6563
_reflns_number_total             7882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           13
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134145
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 Cl3 C35 F1 S1 O2 H51 P1'
_shelx_estimated_absorpt_t_max   0.307
_shelx_estimated_absorpt_t_min   0.227
_reflns_odcompleteness_completeness 99.79
_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
 C28-C27 \\sim C27-C26 \\sim C26-C25 \\sim C25-N1 \\sim N1-C29 \\sim C29-C28
 with sigma of 0.02
 C28-N1 \\sim C28-N1 \\sim C25-C27 \\sim C25-C29 \\sim C29-C27 \\sim N1-C26
 with sigma of 0.04
 C25A-C26A \\sim C26A-C27A \\sim C27A-C28A \\sim C28A-C29A \\sim C29A-N1A \\sim
N1A-C25A
 with sigma of 0.02
 C25A-C29A \\sim C25A-C29A \\sim C28A-C26A \\sim C28A-N1A \\sim N1A-C26A \\sim
C29A-C27A
 with sigma of 0.04
 C30-C32 \\sim C30-C33 \\sim C30-C31
 with sigma of 0.02
 C31-C32 \\sim C31-C33
 with sigma of 0.04
 C30A-C32A \\sim C30A-C31A \\sim C30A-C33A
 with sigma of 0.02
 C33A-C32A \\sim C33A-C31A
 with sigma of 0.04
 C34-Cl3 \\sim C34-Cl1 \\sim C34-Cl2 \\sim C34A_$1-Cl2A_$1 \\sim
C34A_$1-Cl1A_$1 \\sim C34A_$1-
 Cl3A_$1 \\sim C34B_$1-Cl2B_$1 \\sim C34B_$1-Cl3B_$1 \\sim C34B_$1-Cl1B_$1
 with sigma of 0.02
 Cl3-Cl1 \\sim Cl1-Cl2 \\sim Cl2-Cl3 \\sim Cl2A_$1-Cl1A_$1 \\sim
Cl1A_$1-Cl3A_$1 \\sim Cl3A_$1-
 Cl2A_$1 \\sim Cl2B_$1-Cl3B_$1 \\sim Cl3B_$1-Cl1B_$1 \\sim Cl1B_$1-Cl2B_$1
 with sigma of 0.04
 S1A-O2A \\sim S1-O2
 with sigma of 0.02
 S1-O1 \\sim S1A-O1A
 with sigma of 0.02
 Pd1-O1 \\sim Pd1-O1A
 with sigma of 0.02
 S1-C25 \\sim S1A-C25A
 with sigma of 0.02
3. Restrained planarity
 C28, C27, C26, C25, N1, C29
 with sigma of 0.1
 C25A, C26A, C27A, C28A, C29A, N1A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C28 \\sim C27 \\sim C26 \\sim C25 \\sim N1 \\sim C29 \\sim C31 \\sim C30 \\sim
C32 \\sim C33: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim N1A \\sim C33A \\sim
C30A \\sim C32A \\sim C31A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C34 \\sim Cl3 \\sim Cl1 \\sim Cl2: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C34A \\sim Cl2A \\sim Cl1A \\sim Cl3A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C34B \\sim Cl2B \\sim Cl3B \\sim Cl1B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C28, C27, C26, C25, N1, C29, C31, C30, C32, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25A, C26A, C27A, C28A, C29A, N1A, C33A, C30A, C32A, C31A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, Cl3, Cl1, Cl2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34A, Cl2A, Cl1A, Cl3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34B, Cl2B, Cl3B, Cl1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(C34)+Sof(H34)+Sof(Cl3)+Sof(Cl1)+Sof(Cl2)]+1*[Sof(C34A)+Sof(H34A)+
 Sof(Cl2A)+Sof(Cl1A)+Sof(Cl3A)]+1*[Sof(C34B)+Sof(H34B)+Sof(Cl2B)+Sof(Cl3B)+
 Sof(Cl1B)]=1 with esd of 0.0001
 Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=
 Sof(C29A)=Sof(N1A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C30A)=Sof(C32A)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(O2A)=
 Sof(S1A)=Sof(O1A)=1-FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(C28)=Sof(H28)=Sof(C27)=Sof(H27)=Sof(C26)=Sof(H26)=
 Sof(C25)=Sof(N1)=Sof(C29)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C30)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 FVAR(1)
 Sof(C34)=Sof(H34)=Sof(Cl3)=Sof(Cl1)=Sof(Cl2)=FVAR(2)
 Sof(C34A)=Sof(H34A)=Sof(Cl2A)=Sof(Cl1A)=Sof(Cl3A)=FVAR(3)
 Sof(C34B)=Sof(H34B)=Sof(Cl2B)=Sof(Cl3B)=Sof(Cl1B)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C13(H13), C7(H7), C34(H34), C34A(H34A), C34B(H34B)
7.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C16(H16A,H16B), C18(H18A,H18B), C5(H5A,H5B), C17(H17A,H17B),
 C2(H2A,H2B), C14(H14A,H14B), C15(H15A,H15B), C3(H3A,H3B), C4(H4A,H4B),
 C12(H12A,H12B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C10(H10A,H10B)
7.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C24(H24), C21(H21), C23(H23), C28(H28), C27(H27), C26(H26),
 C26A(H26A), C27A(H27A), C28A(H28A)
7.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C33A(H33D,H33E,
 H33F), C32A(H32D,H32E,H32F), C31A(H31D,H31E,H31F)
;
_shelx_res_checksum              50053
_shelx_hkl_checksum              30284
_ins_header
;
TITL 272aim18 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184  12.193172  13.162037  13.465055  64.5677  86.3538  77.9679
ZERR    4.00   0.000658   0.000705   0.000807   0.0055   0.0046   0.0046
LATT  1
SFAC C H O F P S Cl Pd
UNIT 140.00 204.00 8.00 4.00 4.00 4.00 12.00 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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.731