Chiral PCN pincer Ni(ii) complex-catalyzed asymmetric hydrophosphination of 2-alkenoylpyridines with diphenylphosphine
Li, Jin-Ge; Qiu, Bing-Bo; Jiang, Hui; Song, Mao-Ping; Gong, Jun-Fang; RSC Advances 15 (2025) 15904–15918; doi:10.1039/D5RA01336D

data_7250395
_publ_section_title
;
 Chiral PCN pincer Ni(ii) complex-catalyzed asymmetric hydrophosphination
 of 2-alkenoylpyridines with diphenylphosphine
;
_journal_issue                   20
_journal_name_full               'RSC Advances'
_journal_page_first              15904
_journal_page_last               15918
_journal_paper_doi               10.1039/D5RA01336D
_journal_volume                  15
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C41 H34 Cl N2 Ni P'
_chemical_formula_sum            'C41 H34 Cl N2 Ni P'
_chemical_formula_weight         679.83
_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             2023-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-08-07 deposited with the CCDC.	2025-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.90180(14)
_cell_length_b                   16.9395(3)
_cell_length_c                   19.7237(3)
_cell_measurement_reflns_used    6067
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.0170
_cell_measurement_theta_min      4.4540
_cell_volume                     3308.29(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.990
_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    -56.00  37.00   1.00    2.00    --  -33.50  37.00 -90.00   93
  2  \w   -108.00 -35.00   1.00    2.00    --  -33.50 178.00 -90.00   73
  3  \w   -102.00 -15.00   1.00    2.00    --  -33.50 -57.00 -60.00   87
  4  \w     88.00 178.00   1.00    7.50    --  108.00  45.00 150.00   90
  5  \w     50.00 129.00   1.00    7.50    --  108.00 -30.00 120.00   79
  6  \w    127.00 167.00   1.00    7.50    --  108.00  77.00-180.00   40
  7  \w    100.00 147.00   1.00    7.50    --  108.00  30.00 -30.00   47
  8  \w    101.00 174.00   1.00    7.50    --  108.00  77.00 -90.00   73
  9  \w     43.00  69.00   1.00    7.50    --  108.00 -94.00  60.00   26
 10  \w     64.00  94.00   1.00    7.50    --  108.00 -77.00  90.00   30
 11  \w     38.00 107.00   1.00    7.50    --  108.00 -94.00  30.00   69
 12  \w     53.00 121.00   1.00    7.50    --  108.00 -61.00-150.00   68
;
_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      -0.0462034000
_diffrn_orient_matrix_UB_12      0.0775173000
_diffrn_orient_matrix_UB_13      0.0335904000
_diffrn_orient_matrix_UB_21      -0.0150387000
_diffrn_orient_matrix_UB_22      0.0382655000
_diffrn_orient_matrix_UB_23      -0.0704457000
_diffrn_orient_matrix_UB_31      -0.1478277000
_diffrn_orient_matrix_UB_32      -0.0281672000
_diffrn_orient_matrix_UB_33      -0.0033408000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12128
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.470
_diffrn_reflns_theta_min         3.439
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.289
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       prism
_exptl_crystal_F_000             1416
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM and  n-hexane'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 2206 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         6200
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0453P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                5635
_reflns_number_total             6200
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra01336d2.cif
_cod_data_source_block           202307179_auto
_cod_original_cell_volume        3308.29(8)
_cod_database_code               7250395
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C24H28N4P1Cl1Ni1
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.755
_reflns_odcompleteness_completeness 99.94
_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)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B)
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)
2.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C)
;
_shelx_res_checksum              98067
_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 1.244
_oxdiff_exptl_absorpt_empirical_full_min 0.896