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_7250397
_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 rm
_chemical_formula_moiety         'C34 H28 Cl N2 Ni O P'
_chemical_formula_sum            'C34 H28 Cl N2 Ni O P'
_chemical_formula_weight         605.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-04-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-15 deposited with the CCDC.	2025-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.059(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.7861(17)
_cell_length_b                   9.8408(5)
_cell_length_c                   22.2091(17)
_cell_measurement_reflns_used    3594
_cell_measurement_temperature    291.15
_cell_measurement_theta_max      66.4847
_cell_measurement_theta_min      3.2406
_cell_volume                     5946.5(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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  -61.00  -24.00   1.0000    1.4200
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000  -60.0000 37

  2 omega  -75.00  -47.00   1.0000    1.4200
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000   30.0000 28

  3 omega   -6.00   28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000  150.0000 34

  4 omega  -48.00   18.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000    0.0000 66

  5 omega -111.00  -23.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000   30.0000 88

  6 omega  -68.00  -33.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000  150.0000 35

  7 omega   43.00  122.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2266   57.0000 -120.0000 79

  8 omega   52.00   91.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -30.0000 -120.0000 39

  9 omega   92.00  156.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533   45.0000   90.0000 64

 10 omega   41.00   90.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -30.0000  -30.0000 49

 11 omega   41.00   88.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -30.0000   90.0000 47

 12 omega   40.00   93.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -94.0000    0.0000 53

 13 omega  143.00  175.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533   15.0000  -60.0000 32

 14 omega   80.00  123.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533   15.0000  -60.0000 43

 15 omega  132.00  177.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533   61.0000  150.0000 45

 16 omega   45.00  128.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -61.0000    0.0000 83

 17 omega   39.00   93.00   1.0000   34.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4533  -45.0000  150.0000 54

 18 omega   -4.00   42.00   1.0000    1.4200
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   90.0000 46

 19 omega   25.00  116.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2266   77.0000  150.0000 91
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0294075000
_diffrn_orient_matrix_UB_12      0.0364131000
_diffrn_orient_matrix_UB_13      -0.0446529000
_diffrn_orient_matrix_UB_21      -0.0474136000
_diffrn_orient_matrix_UB_22      0.0527639000
_diffrn_orient_matrix_UB_23      -0.0501524000
_diffrn_orient_matrix_UB_31      0.0096659000
_diffrn_orient_matrix_UB_32      0.1427941000
_diffrn_orient_matrix_UB_33      0.0295371000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0758
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11877
_diffrn_reflns_point_group_measured_fraction_full 0.730
_diffrn_reflns_point_group_measured_fraction_max 0.730
_diffrn_reflns_theta_full        66.594
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         3.243
_diffrn_source                   'Enhance (Cu) X-ray Source'
_diffrn_source_current           n/a
_diffrn_source_voltage           n/a
_exptl_absorpt_coefficient_mu    2.503
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'orangish red'
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       block
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1364 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     718
_refine_ls_number_reflns         7666
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0477
_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^)+(0.0415P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1198
_reflns_Friedel_coverage         0.375
_reflns_Friedel_fraction_full    0.426
_reflns_Friedel_fraction_max     0.426
_reflns_number_gt                5954
_reflns_number_total             7666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra01336d2.cif
_cod_data_source_block           201209145
_cod_database_code               7250397
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C20H20N2O4P2Ni1Cl1
_shelx_estimated_absorpt_t_max   0.661
_shelx_estimated_absorpt_t_min   0.573
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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. Uiso/Uaniso restraints and constraints
Uanis(C12') \\sim Ueq, Uanis(C11') \\sim Ueq, Uanis(C9') \\sim Ueq, Uanis(C8')
\\sim Ueq, Uanis(C10') \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.02
Uanis(C8') \\sim Ueq, Uanis(C12') \\sim Ueq, Uanis(C11') \\sim Ueq, Uanis(C10')
\\sim Ueq, Uanis(C9') \\sim Ueq: with sigma of 0 and sigma for terminal atoms
of 0.02
Uanis(C11') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7') = Uanis(C7'A)
Uanis(C8') = Uanis(C8'A)
Uanis(C9') = Uanis(C9'A)
Uanis(C10') = Uanis(C10B)
Uanis(C11') = Uanis(C11B)
Uanis(C12') = Uanis(C12B)
3. Others
 Sof(C9'A)=Sof(H9'A)=Sof(C8'A)=Sof(H8'A)=Sof(C7'A)=Sof(C12B)=Sof(H12B)=
 Sof(C11B)=Sof(H11B)=Sof(C10B)=Sof(H10B)=1-FVAR(1)
 Sof(C7')=Sof(C8')=Sof(H8')=Sof(C9')=Sof(H9')=Sof(C10')=Sof(H10')=Sof(C11')=
 Sof(H11')=Sof(C12')=Sof(H12')=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C21(H21), C21'(H21')
4.b Secondary CH2 refined with riding coordinates:
 C20(H20C,H20D), C20'(H20A,H20B)
4.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), C15(H15), C16(H16), C17(H17), C23(H23), C24(H24), C25(H25), C26(H26),
  C27(H27), C29(H29), C30(H30), C32(H32), C33(H33), C2'(H2'), C3'(H3'),
 C4'(H4'), C5'(H5'), C6'(H6'), C8'(H8'), C9'(H9'), C10'(H10'), C11'(H11'),
 C12'(H12'), C9'A(H9'A), C8'A(H8'A), C12B(H12B), C11B(H11B), C10B(H10B),
 C15'(H15'), C16'(H16'), C17'(H17'), C23'(H23'), C24'(H24'), C25'(H25'),
 C26'(H26'), C27'(H27'), C29'(H29'), C30'(H30'), C32'(H32'), C33'(H33')
4.d Fitted hexagon refined as free rotating group:
 C7'(C8',C9',C10',C11',C12'), C9'A(C8'A,C7'A,C12B,C11B,C10B)
4.e Idealised Me refined as rotating group:
 C34(H34D,H34E,H34F), C34'(H34A,H34B,H34C)
;
_shelx_res_checksum              30574
_olex2_date_sample_data_collection 1347368218.75
_olex2_submission_special_instructions 'No special instructions were received'