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_4134138
_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         '2(C20 H36 O2 P Pd0.5)'
_chemical_formula_sum            'C40 H72 O4 P2 Pd'
_chemical_formula_weight         785.31
_chemical_name_common            Pd(PCy3)2(OAc)2
_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                91.788(2)
_cell_angle_beta                 91.2280(10)
_cell_angle_gamma                91.613(2)
_cell_formula_units_Z            2
_cell_length_a                   9.5870(2)
_cell_length_b                   13.1727(3)
_cell_length_c                   16.0211(3)
_cell_measurement_reflns_used    23117
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.8480
_cell_measurement_theta_min      2.4510
_cell_volume                     2020.96(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     -1.00  42.00   0.50   20.00    --    5.32  20.00  77.00   86
  2  \w    -52.00  16.00   0.50   20.00    --    5.32 -20.00 -89.00  136
  3  \w    -16.00  63.00   0.50   20.00    --   -7.04  38.00-150.00  158
  4  \w    -12.00  65.00   0.50   20.00    --   -7.04  57.00 -90.00  154
  5  \w    -24.00  38.00   0.50   20.00    --    5.32 -99.00-150.00  124
  6  \w    -25.00  15.00   0.50   20.00    --   -7.04 -99.00-120.00   80
  7  \w    -26.00   2.00   0.50   20.00    --   -7.04 -99.00   0.00   56
  8  \w    -26.00   1.00   0.50   20.00    --   -7.04 -99.00  30.00   54
  9  \w    -26.00   9.00   0.50   20.00    --   -7.04 -99.00  90.00   70
 10  \w     -6.00  22.00   0.50   20.00    --   -7.04 -99.00 150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0716183000
_diffrn_orient_matrix_UB_12      -0.0021097000
_diffrn_orient_matrix_UB_13      0.0116805000
_diffrn_orient_matrix_UB_21      -0.0052191000
_diffrn_orient_matrix_UB_22      -0.0538474000
_diffrn_orient_matrix_UB_23      -0.0012132000
_diffrn_orient_matrix_UB_31      0.0180149000
_diffrn_orient_matrix_UB_32      -0.0008264000
_diffrn_orient_matrix_UB_33      -0.0427209000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32404
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.453
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.575
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75931
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       prism
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.464
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     466
_refine_ls_number_reflns         8912
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0260
_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^)+(0.0293P)^2^+1.0341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0641
_refine_ls_wR_factor_ref         0.0659
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7871
_reflns_number_total             8912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13260_si_001.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 4134138--4134148.cif.'
_cod_database_code               4134138
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 O4 C36 P2 H70'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.983
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_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
 C19-O1 \\sim C19-O2
 with sigma of 0.02
 O1-C20 \\sim C20-O2
 with sigma of 0.04
 C19A-O7 \\sim C19A-O8
 with sigma of 0.02
 O7-C20A \\sim C20A-O8
 with sigma of 0.04
3. Restrained planarity
 O1, O2, C19, C20
 with sigma of 0.1
 O7, O8, C19A, C20A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim C19 \\sim C20: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
O7 \\sim O8 \\sim C19A \\sim C20A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 O1, O2, C19, C20
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 O7, O8, C19A, C20A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 Pd2, O3, C39, O4, C40
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
6. Others
 Fixed Sof: O1(0.85) O2(0.85) C19(0.85) C20(0.85) H20A(0.85) H20B(0.85)
 H20C(0.85) O7(0.15) O8(0.15) C19A(0.15) C20A(0.15) H20D(0.15) H20E(0.15)
 H20F(0.15)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C21(H21), C33(H33), C13(H13), C27(H27), C1(H1)
7.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C34(H34A,H34B), C26(H26A,H26B), C18(H18A,H18B), C22(H22A,
 H22B), C28(H28A,H28B), C9(H9A,H9B), C6(H6A,H6B), C15(H15A,H15B), C35(H35A,
 H35B), C25(H25A,H25B), C38(H38A,H38B), C17(H17A,H17B), C23(H23A,H23B), C2(H2A,
 H2B), C12(H12A,H12B), C16(H16A,H16B), C8(H8A,H8B), C5(H5A,H5B), C32(H32A,H32B),
  C24(H24A,H24B), C30(H30A,H30B), C37(H37A,H37B), C31(H31A,H31B), C36(H36A,
 H36B), C29(H29A,H29B), C4(H4A,H4B), C3(H3A,H3B), C10(H10A,H10B), C11(H11A,H11B)
7.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C40(H40A,H40B,H40C), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              23342
_shelx_hkl_checksum              27408
_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 1.559
_oxdiff_exptl_absorpt_empirical_full_min 0.648