Chiral (phosphine)-(imidazoline) PCN pincer palladium(II) complexes: synthesis and application in asymmetric hydrophosphination of 2-alkenoylpyridines with diphenylphosphine
Huang, Jun-Jian; Zhang, Xiao-Qi; Yang, Jing-Jing; Gong, Jun-Fang; Song, Mao-Ping; Dalton Transactions  (2022) –; doi:10.1039/D2DT01078J

data_7710180
_publ_section_title
;
 Chiral (phosphine)-(imidazoline) PCN pincer palladium(II) complexes:
 synthesis and application in asymmetric hydrophosphination of
 2-alkenoylpyridines with diphenylphosphine
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01078J
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C41 H34 Cl N2 P Pd'
_chemical_formula_sum            'C41 H34 Cl N2 P Pd'
_chemical_formula_weight         727.52
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-04-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-23 deposited with the CCDC.	2022-05-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.1047(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.41683(19)
_cell_length_b                   23.3274(3)
_cell_length_c                   12.73072(19)
_cell_measurement_reflns_used    12697
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8160
_cell_measurement_theta_min      3.7570
_cell_volume                     3391.71(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -19.00  21.00   1.00    1.25    --  -33.50  57.00 -30.00   40
  2  \w   -101.00 -19.00   1.00    1.25    --  -33.50 -57.00  90.00   82
  3  \w     -9.00  35.00   1.00    1.25    --  -33.50  19.00 -90.00   44
  4  \w   -100.00 -66.00   1.00    1.25    --  -33.50 178.00  30.00   34
  5  \w    -67.00 -41.00   1.00    1.25    --  -33.50  19.00 -90.00   26
  6  \w     65.00 107.00   1.00    1.25    --   36.47  37.00   0.00   42
  7  \w    -22.00  25.00   1.00    1.25    --   36.47   0.00  60.00   47
  8  \w     12.00  42.00   1.00    1.25    --   36.47  77.00 -60.00   30
  9  \w     84.00 109.00   1.00    1.25    --   36.47 178.00 -60.00   25
 10  \w     52.00 101.00   1.00    1.25    --   36.47  57.00 -60.00   49
 11  \w      9.00  51.00   1.00    1.25    --   36.47  77.00 -30.00   42
 12  \w     55.00  89.00   1.00    1.25    --   36.47  37.00  30.00   34
 13  \w     50.00  84.00   1.00    1.25    --   36.47  77.00 -60.00   34
 14  \w     63.00 108.00   1.00    1.25    --   36.47 178.00 -90.00   45
 15  \w     41.00  74.00   1.00    1.25    --   36.47  37.00 -30.00   33
 16  \w     -2.00  26.00   1.00    1.25    --   36.47  96.00  79.34   28
 17  \w     43.00 107.00   1.00    1.25    --   36.47   0.00  60.00   64
 18  \w     57.00 106.00   1.00    1.25    --   36.47 178.00 -30.00   49
 19  \w      1.00  31.00   1.00    1.25    --   36.47  92.00 -41.53   30
 20  \w      5.00  42.00   1.00    1.25    --   36.47  85.00 171.85   37
 21  \w     69.00 105.00   1.00    1.25    --   36.47 178.00   0.00   36
 22  \w     64.00 109.00   1.00    1.25    --   36.47 178.00 120.00   45
 23  \w    -29.00  56.00   1.00    1.25    --   36.47 -77.00  60.00   85
 24  \w     79.00 109.00   1.00    4.50    --  108.00  77.00 -30.00   30
 25  \w     82.00 108.00   1.00    4.50    --  108.00  30.00   0.00   26
 26  \w    126.00 175.00   1.00    4.50    --  108.00  77.00 -90.00   49
 27  \w     84.00 111.00   1.00    4.50    --  108.00  30.00 -30.00   27
 28  \w     38.00  72.00   1.00    4.50    --  108.00 -94.00 -90.00   34
 29  \w     82.00 109.00   1.00    4.50    --  108.00 -94.00 -90.00   27
 30  \w     82.00 107.00   1.00    4.50    --  108.00  30.00 -60.00   25
 31  \w     88.00 114.00   1.00    4.50    --  108.00  45.00 -60.00   26
 32  \w     80.00 116.00   1.00    4.50    --  108.00  77.00 -90.00   36
 33  \w     64.00  89.00   1.00    4.50    --  108.00  15.00 -30.00   25
 34  \w     88.00 114.00   1.00    4.50    --  108.00  61.00 -90.00   26
 35  \w     47.00 101.00   1.00    4.50    --  108.00 -45.00-120.00   54
 36  \w    100.00 152.00   1.00    4.50    --  108.00 111.00 150.00   52
 37  \w     88.00 114.00   1.00    4.50    --  108.00  45.00   0.00   26
 38  \w    122.00 176.00   1.00    4.50    --  108.00  77.00   0.00   54
 39  \w     79.00 105.00   1.00    4.50    --  108.00  77.00   0.00   26
 40  \w     79.00 105.00   1.00    4.50    --  108.00  77.00  30.00   26
 41  \w     88.00 114.00   1.00    4.50    --  108.00  61.00 -30.00   26
 42  \w    101.00 170.00   1.00    4.50    --  108.00 111.00 120.00   69
 43  \w    109.00 176.00   1.00    4.50    --  108.00  77.00 -60.00   67
 44  \w    125.00 175.00   1.00    4.50    --  108.00 111.00  60.00   50
 45  \w     88.00 114.00   1.00    4.50    --  108.00  61.00 -60.00   26
 46  \w    137.00 167.00   1.00    4.50    --  108.00  61.00  30.00   30
 47  \w     86.00 112.00   1.00    4.50    --  108.00  30.00  60.00   26
 48  \w     88.00 114.00   1.00    4.50    --  108.00  61.00  30.00   26
 49  \w     83.00 110.00   1.00    4.50    --  108.00  30.00  30.00   27
 50  \w    115.00 171.00   1.00    4.50    --  108.00  77.00 -30.00   56
 51  \w     96.00 177.00   1.00    4.50    --  108.00  45.00  60.00   81
 52  \w     88.00 118.00   1.00    4.50    --  108.00  45.00  30.00   30
 53  \w     79.00 104.00   1.00    4.50    --  108.00  77.00 -60.00   25
 54  \w     92.00 118.00   1.00    4.50    --  108.00  45.00 -30.00   26
 55  \w     88.00 114.00   1.00    4.50    --  108.00  61.00   0.00   26
 56  \w     90.00 175.00   1.00    4.50    --  108.00  30.00 120.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0987009000
_diffrn_orient_matrix_UB_12      0.0287583000
_diffrn_orient_matrix_UB_13      -0.0256744000
_diffrn_orient_matrix_UB_21      -0.0715805000
_diffrn_orient_matrix_UB_22      -0.0078537000
_diffrn_orient_matrix_UB_23      -0.1289502000
_diffrn_orient_matrix_UB_31      -0.0576819000
_diffrn_orient_matrix_UB_32      0.0589374000
_diffrn_orient_matrix_UB_33      -0.0046573000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32816
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.950
_diffrn_reflns_theta_min         3.775
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.865
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 4723 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.034(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     831
_refine_ls_number_reflns         12231
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0677P)^2^+1.3398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    0.895
_reflns_Friedel_fraction_max     0.871
_reflns_number_gt                11441
_reflns_number_total             12231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01078j2.cif
_cod_data_source_block           202104105
_cod_original_cell_volume        3391.70(9)
_cod_database_code               7710180
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O5N2Cl1Pd1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.653
_shelx_estimated_absorpt_t_min   0.518
_reflns_odcompleteness_completeness 99.97
_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.a Ternary CH refined with riding coordinates:
 C21(H21), C22(H22), C21'(H21'), C22'(H22')
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13'(H13C,H13D)
2.c 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), C16(H16), C17(H17), C18(H18), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36),
 C37(H37), C39(H39), C40(H40), C2'(H2'), C3'(H3'), C4'(H4'), C5'(H5'), C6'(H6'),
  C8'(H8'), C9'(H9'), C10'(H10'), C11'(H11'), C12'(H12'), C16'(H16'),
 C17'(H17'), C18'(H18'), C24'(H24'), C25'(H25'), C26'(H26'), C27'(H27'),
 C28'(H28'), C30'(H30'), C31'(H31'), C32'(H32'), C33'(H33'), C34'(H34'),
 C36'(H36'), C37'(H37'), C39'(H39'), C40'(H40')
2.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C41'(H41D,H41E,H41F)
;
_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 1.425
_oxdiff_exptl_absorpt_empirical_full_min 0.822