Experimental and Theoretical Studies on the Mechanism of the C‒S Bond Activation of PdII Thiolate/Thioether Complexes
Kumar, Sushil; Guyon, Fabrice; Knorr, Michael; Labat, Stéphane; Miqueu, Karinne; Golz, Christopher; Strohmann, Carsten; Organometallics 36 (2017) 1303–; doi:10.1021/acs.organomet.7b00039

data_4087311
_publ_section_title
;
 Experimental and Theoretical Studies on the Mechanism of the C--S Bond
 Activation of PdII Thiolate/Thioether Complexes
;
_journal_issue                   7
_journal_name_full               Organometallics
_journal_page_first              1303
_journal_paper_doi               10.1021/acs.organomet.7b00039
_journal_volume                  36
_journal_year                    2017
_chemical_formula_moiety         'C26 H21 P Pd S10, 0.5(C H Cl3)'
_chemical_formula_sum            'C26.5 H21.5 Cl1.5 P Pd S10'
_chemical_formula_weight         851.08
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.2309(16)
_cell_angle_beta                 98.3416(17)
_cell_angle_gamma                113.3407(18)
_cell_formula_units_Z            4
_cell_length_a                   13.4247(3)
_cell_length_b                   13.9422(3)
_cell_length_c                   19.6280(4)
_cell_measurement_reflns_used    41671
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      29.9060
_cell_measurement_theta_min      2.6870
_cell_volume                     3329.78(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 16.0560
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -49.00   33.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727  -57.0000   60.0000 82

  2 omega   57.00   83.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727 -134.0000  146.2427 26

  3 omega    3.00   73.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727   57.0000 -120.0000 70

  4 omega    3.00   29.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727 -134.0000  146.2427 26

  5 omega    1.00   87.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727   57.0000  -30.0000 86

  6 omega    1.00   80.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727   57.0000  150.0000 79

  7 omega    2.00   80.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727   57.0000   60.0000 78

  8 omega  -25.00   60.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727  -99.0000 -180.0000 85

  9 omega  -93.00  -54.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  149.0000 -156.3186 39

 10 omega  -40.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102   57.0000  -90.0000 86

 11 omega  -27.00   47.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102   57.0000    0.0000 74

 12 omega    1.00   80.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727 -130.0000   65.6378 79

 13 omega  -25.00   61.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727  -99.0000  -90.0000 86

 14 omega   -6.00   92.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727   38.0000 -150.0000 98

 15 omega  -25.00   21.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -99.0000   30.0000 46

 16 omega  -25.00   21.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -99.0000  -90.0000 46

 17 omega  -91.00   10.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -77.0000  -60.0000 101

 18 omega  -93.00    5.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -38.0000   30.0000 98

 19 omega  -46.00   52.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102   38.0000 -150.0000 98

 20 omega  -97.00  -34.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102 -179.0000 -150.0000 63

 21 omega   34.00   96.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727  179.0000 -180.0000 62

 22 omega  -25.00   61.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       19.4727  -99.0000 -180.0000 86

 23 omega  -25.00   21.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -99.0000   90.0000 46

 24 omega  -89.00    1.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -20.4102  -57.0000 -180.0000 90
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0465850000
_diffrn_orient_matrix_UB_12      0.0482184000
_diffrn_orient_matrix_UB_13      0.0025258000
_diffrn_orient_matrix_UB_21      0.0270741000
_diffrn_orient_matrix_UB_22      -0.0175787000
_diffrn_orient_matrix_UB_23      0.0277520000
_diffrn_orient_matrix_UB_31      0.0222473000
_diffrn_orient_matrix_UB_32      -0.0212182000
_diffrn_orient_matrix_UB_33      -0.0237392000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            116813
_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         26.998
_diffrn_reflns_theta_min         2.469
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.372
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86478
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.698
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1708
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.572
_refine_diff_density_min         -0.692
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         14519
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0245
_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^)+(0.0173P)^2^+3.4074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0528
_refine_ls_wR_factor_ref         0.0556
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12890
_reflns_number_total             14519
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om7b00039_si_002.cif
_cod_data_source_block           compound2
_cod_depositor_comments
;

2026-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C53 H43 Cl3 P2 Pd2 S20'
_cod_original_formula_weight         1702.16
_cod_original_formula_moiety         '2(C26 H21 P Pd S10), C H Cl3'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        3329.79(12)
_cod_database_code               4087311
_chemical_oxdiff_formula         'C20 H20 N2 O4 F3 S1 P2 Fe1 Sn1'
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.684
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C53A) = Uanis(C53B)
Uanis(Cl1B) = Uanis(Cl1A)
3. Others
 Sof(Cl1B)=Sof(C53B)=Sof(H53B)=1-FVAR(1)
 Sof(Cl1A)=Sof(C53A)=Sof(H53A)=FVAR(1)
 Sof(S17B)=Sof(C52B)=Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(2)
 Sof(S17A)=Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C53A(H53A), C53B(H53B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C28(H28), C29(H29),
  C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44)
4.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C48(H48B,H48C,H48A), C52A(H52A,H52B,
 H52C), C52B(H52D,H52E,H52F)
;
_shelx_res_checksum              68537
_shelx_hkl_checksum              51052
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'