PCN Pincer Palladium(II) Complex Catalyzed Enantioselective Hydrophosphination of Enones: Synthesis of Pyridine-Functionalized Chiral Phosphine Oxides as NCsp(3)O Pincer Preligands.
Hao, Xin-Qi; Huang, Juan-Juan; Wang, Tao; Lv, Jing; Gong, Jun-Fang; Song, Mao-Ping; The Journal of organic chemistry 79 (2014) 9512–9530; doi:10.1021/jo5015307

data_4029972
_publ_section_title
;
 PCN Pincer Palladium(II) Complex Catalyzed Enantioselective
 Hydrophosphination of Enones: Synthesis of Pyridine-Functionalized Chiral
 Phosphine Oxides as NCsp(3)O Pincer Preligands.
;
_journal_issue                   20
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9512
_journal_page_last               9530
_journal_paper_doi               10.1021/jo5015307
_journal_volume                  79
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H28 Cl N2 O P Pd, C4 O, 0.13(O)'
_chemical_formula_sum            'C38 H38.25 Cl N2 O2.13 P Pd'
_chemical_formula_weight         729.78
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-10
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:20:19, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.8910(4)
_cell_length_b                   16.1795(3)
_cell_length_c                   10.0364(3)
_cell_measurement_reflns_used    5920
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      26.3135
_cell_measurement_theta_min      3.0791
_cell_volume                     3392.36(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   38.00   82.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       19.9448  178.0000 -120.0000 44

  2 omega    3.00   77.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       19.9448   57.0000   90.0000 74

  3 omega   -3.00   73.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       19.9448   37.0000   30.0000 76

  4 omega  -50.00  -25.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       19.9448  -77.0000  -30.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0097993000
_diffrn_orient_matrix_UB_12      -0.0381527000
_diffrn_orient_matrix_UB_13      -0.0285078000
_diffrn_orient_matrix_UB_21      -0.0320260000
_diffrn_orient_matrix_UB_22      0.0080933000
_diffrn_orient_matrix_UB_23      0.0196979000
_diffrn_orient_matrix_UB_31      -0.0057568000
_diffrn_orient_matrix_UB_32      0.0201816000
_diffrn_orient_matrix_UB_33      -0.0615400000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            14040
_diffrn_reflns_theta_full        26.35
_diffrn_reflns_theta_max         26.35
_diffrn_reflns_theta_min         3.08
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_source_current           n/a
_diffrn_source_voltage           n/a
_exptl_absorpt_coefficient_mu    0.709
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1501
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     412
_refine_ls_number_reflns         6907
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0529
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0463P)^2^+0.8197P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0911
_refine_ls_wR_factor_ref         0.0968
_reflns_number_gt                6022
_reflns_number_total             6907
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5015307_si_002.cif
_cod_data_source_block           complex-IX
_cod_depositor_comments
'Adding full bibliography for 4029972--4029973.cif.'
_cod_database_code               4029972
_chemical_oxdiff_formula         C20H20N4O1P1Pd1Cl1
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H13 of C13, H5 of C5, H24 of C24, H20 of C20, H11 of C11, H33 of C33, H34
  of C34, H9 of C9, H32 of C32, H31 of C31, H3 of C3, H30 of C30, H15 of C15,
  {H8A,H8B} of C8, H4 of C4, H14 of C14, H21 of C21, H17 of C17, H28 of C28,
  H18 of C18, H25 of C25, H27 of C27, H12 of C12, H26 of C26
 At 1.5 times of:
  {H22A,H22B,H22C} of C22
2. Restrained distances
 C37-C38
 1.6 with sigma of 0.02
 O3-C37
 1.45 with sigma of 0.02
 O3-C35
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C38) ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: O2(0.125)
5.a Ternary CH refined with riding coordinates:
 C9(H9)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
5.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C28(H28), C18(H18), C30(H30), C12(H12), C15(H15), C3(H3), C24(H24),
 C21(H21), C14(H14), C5(H5), C34(H34), C33(H33), C13(H13), C11(H11), C20(H20),
 C31(H31), C32(H32), C4(H4), C27(H27), C25(H25), C26(H26)
5.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;