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_7250396
_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 O2 P S, C H2 Cl2'
_chemical_formula_sum            'C42 H36 Cl3 N2 Ni O2 P S'
_chemical_formula_weight         828.82
_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     heavy
_audit_creation_date             2023-07-25
_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                   10.22391(12)
_cell_length_b                   13.99060(16)
_cell_length_c                   26.8623(3)
_cell_measurement_reflns_used    7106
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.3690
_cell_measurement_theta_min      4.5490
_cell_volume                     3842.35(8)
_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    -33.00  29.00   0.50    2.50    --  -33.50  57.00 -30.00  124
  2  \w   -101.00 -36.00   0.50    2.50    --  -33.50 178.00 -30.00  130
  3  \w    -82.00 -15.00   0.50    2.50    --  -33.50 -57.00-120.00  134
  4  \w    -90.00 -16.00   0.50    2.50    --  -33.50 -57.00  30.00  148
  5  \w     70.00 110.00   0.50    2.50    --   36.47 178.00 -90.00   80
  6  \w     41.00  99.00   0.50   12.50    --  108.00-110.00  60.00  116
  7  \w     57.00 104.00   0.50   12.50    --  108.00 -94.00-180.00   94
  8  \w    102.00 146.00   0.50   12.50    --  108.00  77.00 150.00   88
  9  \w    108.00 133.00   0.50   12.50    --  108.00  77.00 -90.00   50
 10  \w     38.00 128.00   0.50   12.50    --  108.00 -45.00  60.00  180
 11  \w     85.00 178.00   0.50   12.50    --  108.00  30.00  60.00  186
 12  \w     47.00 128.00   0.50   12.50    --  108.00 -61.00-120.00  162
 13  \w    111.00 171.00   0.50   12.50    --  108.00 111.00-150.00  120
;
_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      -0.0523134000
_diffrn_orient_matrix_UB_12      0.0325121000
_diffrn_orient_matrix_UB_13      0.0510521000
_diffrn_orient_matrix_UB_21      0.0178488000
_diffrn_orient_matrix_UB_22      -0.1021533000
_diffrn_orient_matrix_UB_23      0.0202969000
_diffrn_orient_matrix_UB_31      0.1401754000
_diffrn_orient_matrix_UB_32      0.0251500000
_diffrn_orient_matrix_UB_33      0.0164608000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            14376
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.440
_diffrn_reflns_theta_min         3.562
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.860
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92371
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_description       prism
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.341
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 2612 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         7194
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0412
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0597P)^2^+0.4620P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1044
_refine_ls_wR_factor_ref         0.1086
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                6605
_reflns_number_total             7194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra01336d2.cif
_cod_data_source_block           202307191_auto
_cod_original_cell_volume        3842.34(8)
_cod_database_code               7250396
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4P1S1Cl1Ni1
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.634
_reflns_odcompleteness_completeness 99.90
_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), C42(H42A,H42B)
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              20341
_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 1.158
_oxdiff_exptl_absorpt_empirical_full_min 0.919