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_7710178
_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         'C35 H30 Cl N2 O P Pd'
_chemical_formula_sum            'C35 H30 Cl N2 O P Pd'
_chemical_formula_weight         667.43
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-01-06
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.20754(8)
_cell_length_b                   14.47998(12)
_cell_length_c                   22.6523(2)
_cell_measurement_reflns_used    10558
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8460
_cell_measurement_theta_min      4.9330
_cell_volume                     3020.12(5)
_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 1.000
_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    -61.00 -18.00   1.00    1.00    --  -33.50  77.00 120.00   43
  2  \w      0.00  36.00   1.00    1.00    --  -33.50  77.00 120.00   36
  3  \w    -79.00 -16.00   1.00    1.00    --  -33.50 -57.00  60.00   63
  4  \w    -93.00 -26.00   1.00    1.00    --  -33.50 -57.00 120.00   67
  5  \w     59.00 105.00   1.00    1.00    --   36.47  57.00 -30.00   46
  6  \w     32.00  77.00   1.00    1.00    --   36.47 -99.00 -60.00   45
  7  \w     70.00  96.00   1.00    1.00    --   36.47  37.00  60.00   26
  8  \w    -21.00  31.00   1.00    1.00    --   36.47 -57.00 -90.00   52
  9  \w    -12.00  55.00   1.00    1.00    --   36.47 -57.00 -60.00   67
 10  \w     36.00  65.00   1.00    1.00    --   36.47 -77.00  30.00   29
 11  \w     58.00 107.00   1.00    1.00    --   36.47 178.00 -90.00   49
 12  \w     60.00  92.00   1.00    1.00    --   36.47 178.00-120.00   32
 13  \w     12.00  58.00   1.00    1.00    --   36.47 -37.00 -30.00   46
 14  \w    -31.00  13.00   1.00    1.00    --   36.47 -77.00  30.00   44
 15  \w    -18.00  37.00   1.00    1.00    --   36.47 -57.00  60.00   55
 16  \w     73.00 102.00   1.00    1.00    --   36.47-154.00  55.00   29
 17  \w     19.00  50.00   1.00    1.00    --   36.47  37.00  60.00   31
 18  \w     62.00 111.00   1.00    4.50    --  108.00 -61.00-150.00   49
 19  \w    100.00 174.00   1.00    4.50    --  108.00  45.00-150.00   74
 20  \w    100.00 172.00   1.00    4.50    --  108.00  61.00  60.00   72
 21  \w     46.00 135.00   1.00    4.50    --  108.00 -77.00-180.00   89
 22  \w     79.00 174.00   1.00    4.50    --  108.00  77.00   0.00   95
 23  \w    103.00 129.00   1.00    4.50    --  108.00 111.00-180.00   26
 24  \w     90.00 137.00   1.00    4.50    --  108.00-154.00  55.00   47
 25  \w     38.00 110.00   1.00    4.50    --  108.00 -94.00   0.00   72
 26  \w     45.00 121.00   1.00    4.50    --  108.00 -45.00 -30.00   76
 27  \w     94.00 174.00   1.00    4.50    --  108.00  61.00  30.00   80
 28  \w    102.00 127.00   1.00    4.50    --  108.00 111.00 -90.00   25
 29  \w     56.00  96.00   1.00    4.50    --  108.00 -94.00  90.00   40
 30  \w     72.00 107.00   1.00    4.50    --  108.00 -94.00 120.00   35
 31  \w     96.00 177.00   1.00    4.50    --  108.00  45.00 150.00   81
 32  \w     38.00 125.00   1.00    4.50    --  108.00 -45.00  60.00   87
 33  \w     44.00  78.00   1.00    4.50    --  108.00-154.00  55.00   34
;
_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      0.0513621000
_diffrn_orient_matrix_UB_12      -0.0258357000
_diffrn_orient_matrix_UB_13      -0.0625900000
_diffrn_orient_matrix_UB_21      0.0064668000
_diffrn_orient_matrix_UB_22      -0.1024428000
_diffrn_orient_matrix_UB_23      0.0181640000
_diffrn_orient_matrix_UB_31      -0.1590861000
_diffrn_orient_matrix_UB_32      -0.0125079000
_diffrn_orient_matrix_UB_33      -0.0194723000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            22452
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.623
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.508
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84490
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 2145 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.030(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         5374
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0279
_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^)+(0.0424P)^2^+0.2700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0694
_refine_ls_wR_factor_ref         0.0712
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5128
_reflns_number_total             5374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01078j2.cif
_cod_data_source_block           20210107
_cod_database_code               7710178
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N4Cl1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.592
_shelx_estimated_absorpt_t_min   0.485
_reflns_odcompleteness_completeness 99.93
_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:
 C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C21(H21A,H21B)
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), C18(H18), C17(H17), C16(H16), C28(H28), C27(H27), C26(H26), C25(H25),
  C24(H24), C30(H30), C31(H31), C33(H33), C34(H34)
2.d Fitted hexagon refined as free rotating group:
 C14(C19,C18,C17,C16,C15), C23(C28,C27,C26,C25,C24)
2.e Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C)
;
_shelx_res_checksum              93950
_shelx_hkl_checksum              87523
_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 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.887