Enantioselective Hydrophosphination of Enones with Diphenylphosphine Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes
Hao, Xin-Qi; Zhao, Yong-Wei; Yang, Jing-Jing; Niu, Jun-Long; Gong, Jun-Fang; Song, Mao-Ping; Organometallics 33 (2014) 1801–; doi:10.1021/om500144b

data_4082883
_publ_section_title
;
 Enantioselective Hydrophosphination of Enones with Diphenylphosphine
 Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes
;
_journal_issue                   7
_journal_name_full               Organometallics
_journal_page_first              1801
_journal_paper_doi               10.1021/om500144b
_journal_volume                  33
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C100 H82 Cl4 N10 O4 Pd2, 3(C H2 Cl2)'
_chemical_formula_sum            'C103 H88 Cl10 N10 O4 Pd2'
_chemical_formula_weight         2097.13
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-17
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.7630(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   16.1148(2)
_cell_length_b                   18.9167(3)
_cell_length_c                   16.4436(2)
_cell_measurement_reflns_used    7951
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.3200
_cell_measurement_theta_min      3.9270
_cell_volume                     5006.82(12)
_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
;
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
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -61.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  150.0000 27

  2 omega   11.00   37.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000  -30.0000 26

  3 omega  -42.00   28.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  150.0000 70

  4 omega  -46.00  -14.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  -30.0000 32

  5 omega  -55.00   28.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   45.0000    0.0000 83

  6 omega  -32.00   26.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000 -180.0000 58

  7 omega -115.00  -42.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -19.0000 -180.0000 73

  8 omega   41.00   90.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   30.0000 49

  9 omega   39.00   66.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -180.0000 27

 10 omega   93.00  177.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000    0.0000 84

 11 omega   50.00   90.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -90.0000 40

 12 omega   47.00   86.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -150.0000 39

 13 omega   51.00   86.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   90.0000 35

 14 omega   47.00   79.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000    0.0000 32

 15 omega   55.00   95.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  -60.0000 40

 16 omega   59.00   90.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   60.0000 31

 17 omega   61.00  178.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -30.0000 117

 18 omega  -72.00   26.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -37.0000  -60.0000 98
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0488563000
_diffrn_orient_matrix_UB_12      0.0389460000
_diffrn_orient_matrix_UB_13      0.0692481000
_diffrn_orient_matrix_UB_21      -0.0387926000
_diffrn_orient_matrix_UB_22      -0.0487799000
_diffrn_orient_matrix_UB_23      0.0628699000
_diffrn_orient_matrix_UB_31      0.0725827000
_diffrn_orient_matrix_UB_32      -0.0523133000
_diffrn_orient_matrix_UB_33      -0.0070420000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            18313
_diffrn_reflns_theta_full        67.08
_diffrn_reflns_theta_max         67.08
_diffrn_reflns_theta_min         3.56
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.795
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70701
_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
;
;
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             2140
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.771
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.020(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1155
_refine_ls_number_reflns         12456
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0723P)^2^+1.8256P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1197
_reflns_number_gt                11393
_reflns_number_total             12456
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om500144b_si_002.cif
_cod_data_source_block           complex-3
_cod_depositor_comments          'Adding full bibliography for 4082883.cif.'
_cod_database_code               4082883
_chemical_oxdiff_formula         C20H20N4O4Pd1
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C103-Cl10
 1.7 with sigma of 0.02
 C103-Cl9
 1.7 with sigma of 0.02
 C1-C2 = C3-C4 = C5-C6
 1.39 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C99) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C58(H58), C8(H8), C93(H93), C57(H57), C94(H94), C7(H7), C44(H44), C43(H43)
4.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C103(H10E,H10F), C102(H10C,H10D)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C77(H77), C23(H23), C25(H25), C75(H75), C73(H73), C51(H51),
 C50(H50), C55(H55), C96(H96), C34(H34), C16(H16), C82(H82), C20(H20), C60(H60),
  C10(H10), C41(H41), C66(H66), C69(H69), C35(H35), C85(H85), C87(H87),
 C70(H70), C53(H53), C84(H84), C54(H54), C91(H91), C62(H62), C64(H64), C14(H14),
  C63(H63), C98(H98), C88(H88), C40(H40), C17(H17), C89(H89), C97(H97),
 C48(H48), C19(H19), C67(H67), C47(H47), C100(H100), C32(H32), C81(H81),
 C52(H52), C31(H31), C46(H46), C90(H90), C61(H61), C1(H1), C2(H2), C3(H3),
 C4(H4), C5(H5), C37(H37), C49(H49), C11(H11), C38(H38), C13(H13), C12(H12),
 C39(H39), C99(H99)
4.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6)
4.e Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C86(H86A,H86B,H86C), C21(H21A,H21B,H21C), C36(H36A,H36B,
 H36C)
;