ModularP-Chirogenic Phosphine-Sulfide Ligands: Clear Evidence for Both Electronic Effect andP-Chirality Driving Enantioselectivity in Palladium-Catalyzed Allylations
Bayardon, Jérôme; Maronnat, Milène; Langlois, Adam; Rousselin, Yoann; Harvey, Pierre D.; Jugé, Sylvain; Organometallics 34 (2015) 4340–; doi:10.1021/acs.organomet.5b00585

data_4087766
_publ_section_title
;
 ModularP-Chirogenic Phosphine-Sulfide Ligands: Clear Evidence for Both
 Electronic Effect andP-Chirality Driving Enantioselectivity in
 Palladium-Catalyzed Allylations
;
_journal_issue                   17
_journal_name_full               Organometallics
_journal_page_first              4340
_journal_paper_doi               10.1021/acs.organomet.5b00585
_journal_volume                  34
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H21 Cl2 O P Pd S, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C25.5 H22 Cl3 O P Pd S'
_chemical_formula_weight         620.21
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-10-25
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_audit_update_record
;
2013-10-25 # Formatted by publCIF

;
_cell_angle_alpha                79.599(3)
_cell_angle_beta                 83.726(3)
_cell_angle_gamma                76.827(3)
_cell_formula_units_Z            2
_cell_length_a                   8.7467(5)
_cell_length_b                   10.6016(6)
_cell_length_c                   14.2035(9)
_cell_measurement_temperature    115
_cell_volume                     1258.15(13)
_computing_cell_refinement
;
Bruker (2013). <i>SAINT</i>. Bruker AXS Inc., Madison, Wisconsin, USA.
;
_computing_data_collection
;
Bruker (2013). <i>APEX2</i>.Bruker AXS Inc., Madison, Wisconsin, USA.
;
_computing_data_reduction
;
Bruker (2013). <i>SAINT</i>. Bruker AXS Inc., Madison, Wisconsin, USA.
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      115.0
_diffrn_detector                 'CCD Plate'
_diffrn_detector_area_resol_mean 9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Nonius Kappa Apex II'
_diffrn_measurement_method       'CCD rotation images, thick slices'
_diffrn_radiation_collimation    '0.6 mm'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a~1~'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0605
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            49530
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.581
_diffrn_reflns_theta_min         1.461
_diffrn_source                   'X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens KFF Mo 2K-180'
_exptl_absorpt_coefficient_mu    1.220
_exptl_absorpt_correction_T_max  0.74
_exptl_absorpt_correction_T_min  0.65
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SABABS
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.637
_exptl_crystal_description       plate
_exptl_crystal_F_000             622
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and ether by slow evaporation'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.186
_refine_diff_density_min         -1.541
_refine_diff_density_rms         0.112
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    36
_refine_ls_number_parameters     535
_refine_ls_number_reflns         11528
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0016P)^2^+3.0747P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0697
_refine_ls_wR_factor_ref         0.0765
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                9478
_reflns_number_total             11528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00585_si_001.cif
_cod_data_source_block           13jb0702
_cod_depositor_comments
;

2026-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C51 H44 Cl6 O2 P2 Pd2 S2'
_cod_original_formula_weight         1240.42
_cod_original_formula_moiety         '2(C25 H21 Cl2 O P Pd S), C H2 Cl2'
_cod_original_formula_units_Z            1
_cod_database_code               4087766
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.792
_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. Uiso/Uaniso restraints and constraints
Uanis(Pd1) = Uanis(Pd1B) = Uanis(Cl2) = Uanis(Cl2B) = Uanis(S1) = Uanis(S1B) =
Uanis(C1B) = Uanis(C2B) = Uanis(C3B) = Uanis(C4B) = Uanis(C5B) = Uanis(C6B) =
Uanis(C21) = Uanis(C20) = Uanis(C22) = Uanis(C23) = Uanis(C24) = Uanis(C25) =
Uanis(Cl1) = Uanis(Cl1B)
Uanis(Cl3B) = Uanis(S2B) = Uanis(C31B) = Uanis(C30B) = Uanis(C29B) =
Uanis(C28B) = Uanis(C27B) = Uanis(C26B) = Uanis(Cl1A) = Uanis(S1A) =
Uanis(C20A) = Uanis(C25A) = Uanis(C24A) = Uanis(C23A) = Uanis(C22A) =
Uanis(C21A)
3. Others
 Fixed Sof: C1B(0.2) C2B(0.2) H2B(0.2) C3B(0.2) H3B(0.2) C4B(0.2) H4B(0.2)
 C5B(0.2) HC(0.2) C6B(0.2) HD(0.2) C20(0.8) C21(0.8) H21(0.8) C22(0.8) HI(0.8)
 C23(0.8) HJ(0.8) C24(0.8) HK(0.8) C25(0.8) HL(0.8) S1(0.8) S1B(0.2) Cl1(0.8)
 Cl1B(0.2) Cl2(0.8) Cl2B(0.2) Pd1(0.8) Pd1B(0.2) C20A(0.8) C21A(0.8) H21A(0.8)
 C22A(0.8) H22A(0.8) C23A(0.8) H23A(0.8) C24A(0.8) H24A(0.8) C25A(0.8)
 H25A(0.8) C26B(0.2) H26B(0.2) C27B(0.2) HW(0.2) C28B(0.2) HX(0.2) C29B(0.2)
 HY(0.2) C30B(0.2) H30B(0.2) C31B(0.2) S1A(0.8) S2B(0.2) Cl1A(0.8) Cl3B(0.2)
 C26(0.8) H26A(0.8) H26C(0.8) Cl5(0.8) Cl6(0.8) C26*(0.2) HZ(0.2) H1(0.2) Cl5*
 (0.2) Cl6*(0.2)
4.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26C), C26*(HZ,H1)
4.b Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C3B(H3B), C4B(H4B), C5B(HC), C6B(HD), C3(HE), C4(HF), C5(HG),
 C6(HH), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C17(H17),
 C18(H18), C19(H19), C21(H21), C22(HI), C23(HJ), C24(HK), C25(HL), C3A(HP),
 C4A(HQ), C5A(HR), C6A(HS), C9A(H9A), C10A(H10A), C11A(HT), C12A(HU), C13A(HV),
 C14A(H14A), C17A(H17A), C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A),
 C23A(H23A), C24A(H24A), C25A(H25A), C26B(H26B), C27B(HW), C28B(HX), C29B(HY),
 C30B(H30B)
4.c Fitted hexagon refined as free rotating group:
 C1B(C2B,C3B,C4B,C5B,C6B), C26B(C27B,C28B,C29B,C30B,C31B)
4.d Idealised Me refined as rotating group:
 C1(H,HA,HB), C1A(HM,HN,HO)
;
_shelx_res_checksum              13922
_shelx_hkl_checksum              68318