Electrosynthesis of iminophosphoranes and applications in nickel catalysis.
Mdluli, Velabo; Lehnherr, Dan; Lam, Yu-Hong; Chaudhry, Mohammad T.; Newman, Justin A.; DaSilva, Jimmy O.; Regalado, Erik L.; Chemical science 15 (2024) 5980–5992; doi:10.1039/d3sc05357a

data_1571200
_publ_section_title
;
 Electrosynthesis of iminophosphoranes and applications in nickel
 catalysis.
;
_journal_issue                   16
_journal_name_full               'Chemical science'
_journal_page_first              5980
_journal_page_last               5992
_journal_paper_doi               10.1039/d3sc05357a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '1(C20 H17 N4 P)'
_chemical_formula_sum            'C20 H17 N4 P'
_chemical_formula_weight         344.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-04-27 deposited with the CCDC.	2024-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.840(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.8140(3)
_cell_length_b                   14.2764(2)
_cell_length_c                   14.7633(2)
_cell_measurement_reflns_used    20486
_cell_measurement_temperature    297.42(10)
_cell_measurement_theta_max      76.8330
_cell_measurement_theta_min      2.5940
_cell_volume                     3574.06(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.933
_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    -69.00  22.00   0.50    0.16    --  -50.08  74.00  63.00  182
  2  \w    -93.00 -18.00   0.50    0.64    --  -90.00  74.00  63.00  150
  3  \w    -65.00 -18.00   0.50    0.64    --  -90.00  57.00  60.00   94
  4  \w    -65.00 -39.00   0.50    0.64    --  -90.00  57.00   0.00   52
  5  \w    -46.00 -18.00   0.50    0.64    --  -90.00  38.00   0.00   56
  6  \w    -46.00 -18.00   0.50    0.64    --  -90.00  38.00 -90.00   56
  7  \w    -46.00 -21.00   0.50    0.64    --  -90.00  38.00-150.00   50
  8  \w    -43.00 -18.00   0.50    0.64    --  -90.00  38.00-180.00   50
  9  \w    -33.00  23.00   0.50    0.16    --  -50.08  19.00-150.00  112
 10  \w   -122.00 -31.00   0.50    0.16    --  -50.08 -74.00 -65.00  182
 11  \w   -161.00-111.00   0.50    0.64    --  -90.00 -57.00-120.00  100
 12  \w   -159.00-133.00   0.50    0.64    --  -90.00 -74.00 -65.00   52
 13  \w   -161.00-116.00   0.50    0.64    --  -90.00 -57.00 -30.00   90
 14  \w   -161.00-128.00   0.50    0.64    --  -90.00 -57.00  30.00   66
 15  \w   -145.00-112.00   0.50    0.64    --  -90.00 -99.00   0.00   66
 16  \w   -159.00-114.00   0.50    0.64    --  -90.00 -99.00-150.00   90
 17  \w    -21.00  70.00   0.50    0.16    --   50.08 -74.00 -65.00  182
 18  \w     35.00  91.00   0.50    0.64    --  107.23 -74.00 -65.00  112
 19  \w     37.00  63.00   0.50    0.64    --  107.23 -57.00 -30.00   52
 20  \w     37.00  63.00   0.50    0.64    --  107.23 -57.00   0.00   52
 21  \w     36.00  64.00   0.50    0.64    --  107.23 -57.00-180.00   56
 22  \w    -22.00  31.00   0.50    0.16    --   50.08 -19.00 -60.00  106
 23  \w     35.00  60.00   0.50    0.64    --  107.23 -57.00  90.00   50
 24  \w     35.00  60.00   0.50    0.64    --  107.23 -57.00 120.00   50
 25  \w    118.00 178.00   0.50    0.64    --  107.23  57.00 150.00  120
 26  \w     88.00 178.00   0.50    0.64    --  107.23  74.00  63.00  180
 27  \w     31.00 122.00   0.50    0.16    --   50.08  74.00  63.00  182
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0095668000
_diffrn_orient_matrix_UB_12      0.0879799000
_diffrn_orient_matrix_UB_13      -0.0558728000
_diffrn_orient_matrix_UB_21      0.0896160000
_diffrn_orient_matrix_UB_22      -0.0014590000
_diffrn_orient_matrix_UB_23      0.0502209000
_diffrn_orient_matrix_UB_31      0.0115616000
_diffrn_orient_matrix_UB_32      -0.0624399000
_diffrn_orient_matrix_UB_33      -0.0797909000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            33748
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.435
_diffrn_reflns_theta_min         2.606
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.428
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.775
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.280
_exptl_crystal_description       plate
_exptl_crystal_F_000             1440
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile, acetone, hexane'
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.031
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         7085
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0428
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0581P)^2^+0.5289P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1047
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6049
_reflns_number_total             7085
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05357a2.cif
_cod_data_source_block           Compound_4
_cod_depositor_comments
'Adding full bibliography for 1571196--1571204.cif.'
_cod_database_code               1571200
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H18N4P
_shelx_estimated_absorpt_t_max   0.866
_shelx_estimated_absorpt_t_min   0.719
_olex2_refinement_description
;
1. Restrained distances
 C7A-C8A \\sim C7A-C1
 with sigma of 0.02
 C7A-C12A \\sim C7A-C4
 with sigma of 0.02
 C8A-C9A \\sim C1-C2
 with sigma of 0.02
 C7A-C11A \\sim C7A-C3
 with sigma of 0.04
 C10A-C12A \\sim C10A-C4
 with sigma of 0.04
 C9A-C10A \\sim C2-C10A
 with sigma of 0.02
 C7A-C9A \\sim C7A-C2
 with sigma of 0.04
 C8A-C10A \\sim C1-C10A
 with sigma of 0.04
 C10A-C11A \\sim C10A-C3
 with sigma of 0.02
 C11A-C12A \\sim C3-C4
 with sigma of 0.02
 P1B-C18B \\sim P1B-C18C
 with sigma of 0.04
 C14B-C16B \\sim C14C-C16C
 with sigma of 0.04
 N1B-N3B \\sim N1B-N3C
 with sigma of 0.04
 C16B-C18B \\sim C16C-C18C
 with sigma of 0.04
 N3B-N4B \\sim N3C-N4C
 with sigma of 0.04
 P1B-C13B \\sim P1B-C13C
 with sigma of 0.02
 C13B-C17B \\sim C13C-C17C
 with sigma of 0.04
 N1B-C19B \\sim N1B-C19C
 with sigma of 0.02
 N2B-C19B \\sim N2C-C19C
 with sigma of 0.02
 N3B-C19B \\sim N3C-C19C
 with sigma of 0.02
 P1B-C14B \\sim P1B-C14C
 with sigma of 0.04
 N3B-C20B \\sim N3C-C20C
 with sigma of 0.02
 N1B-N2B \\sim N1B-N2C
 with sigma of 0.04
 N4B-C20B \\sim N4C-C20C
 with sigma of 0.02
 N2B-N3B \\sim N2C-N3C
 with sigma of 0.04
 C13B-C14B \\sim C13C-C14C
 with sigma of 0.02
 C13B-C18B \\sim C13C-C18C
 with sigma of 0.02
 C13B-C15B \\sim C13C-C15C
 with sigma of 0.04
 C14B-C15B \\sim C14C-C15C
 with sigma of 0.02
 C15B-C16B \\sim C15C-C16C
 with sigma of 0.02
 C14B-C18B \\sim C14C-C18C
 with sigma of 0.04
 C16B-C17B \\sim C16C-C17C
 with sigma of 0.02
 C15B-C17B \\sim C15C-C17C
 with sigma of 0.04
 C17B-C18B \\sim C17C-C18C
 with sigma of 0.02
 C19B-C20B \\sim C19C-C20C
 with sigma of 0.04
2. Others
 Sof(H10C)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=1-
 FVAR(1)
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=
 Sof(H12A)=FVAR(1)
 Sof(N4C)=Sof(C20C)=Sof(N3C)=Sof(C19C)=Sof(N2C)=Sof(H2CA)=Sof(H2CB)=Sof(C13C)=
 Sof(C14C)=Sof(H14C)=Sof(C15C)=Sof(H15C)=Sof(C16C)=Sof(H16C)=Sof(C17C)=
 Sof(H17C)=Sof(C18C)=Sof(H18C)=1-FVAR(2)
 Sof(N2B)=Sof(H2BA)=Sof(H2BB)=Sof(N3B)=Sof(N4B)=Sof(C13B)=Sof(C14B)=Sof(H14B)=
 Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=
 Sof(H18B)=Sof(C19B)=Sof(C20B)=FVAR(2)
3.a Rotating group:
 N2B(H2BA,H2BB), N2C(H2CA,H2CB)
3.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C8A(H8A), C9A(H9A),
 C10A(H10A), C10A(H10C), C11A(H11A), C12A(H12A), C14A(H14A), C15A(H15A),
 C16A(H16A), C17A(H17A), C18A(H18A), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B),
 C6B(H6B), C8B(H8B), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C14B(H14B),
 C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B), C1(H1), C2(H2), C3(H3), C4(H4),
  C14C(H14C), C15C(H15C), C16C(H16C), C17C(H17C), C18C(H18C)
3.c X=CH2 refined with riding coordinates:
 N2A(H2AA,H2AB)
;
_shelx_res_checksum              12962
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.184
_oxdiff_exptl_absorpt_empirical_full_min 0.832