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_1571202
_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         'C48 H37 Br3 N7 Ni2 O P2, Br, 1[N1H3C2]'
_chemical_formula_sum            'C49 H40 Br4 N9 Ni2 O P2'
_chemical_formula_weight         1269.90
_chemical_name_systematic        mds322
_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   geom
_audit_creation_date             2023-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-30 deposited with the CCDC.	2024-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.658(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0937(3)
_cell_length_b                   27.1340(6)
_cell_length_c                   15.1168(3)
_cell_measurement_reflns_used    18900
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.1180
_cell_measurement_theta_min      2.5890
_cell_volume                     4799.14(19)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.999
_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    -31.00  14.00   0.50   46.46    --   -6.11 -80.00  99.00   90
  2  \w    -29.00  -4.00   0.50   46.46    --   -6.11  80.00-136.00   50
  3  \w    -41.00  13.00   0.50   46.46    --    7.21 -80.00  99.00  108
  4  \w    -28.00  11.00   0.50   46.46    --   -6.11  77.00 120.00   78
  5  \w    -10.00  16.00   0.50   46.46    --   -6.11 -77.00 -60.00   52
  6  \w    -27.00  14.00   0.50   46.46    --   -6.11  73.00 -46.82   82
  7  \w    -11.00  15.00   0.50   46.46    --   -6.11 -77.00-180.00   52
  8  \w     -9.00  17.00   0.50   46.46    --   -6.11 -77.00-150.00   52
  9  \w      7.00  41.00   0.50   46.46    --    7.21 -99.00-120.00   68
 10  \w     -8.00  20.00   0.50   46.46    --    7.21  57.00-150.00   56
 11  \w     14.00  39.00   0.50   46.46    --    7.21 -99.00 -30.00   50
 12  \w      6.00  31.00   0.50   46.46    --    7.21 -99.00 -90.00   50
;
_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      -0.0309306000
_diffrn_orient_matrix_UB_12      -0.0212175000
_diffrn_orient_matrix_UB_13      0.0070583000
_diffrn_orient_matrix_UB_21      -0.0461015000
_diffrn_orient_matrix_UB_22      0.0071024000
_diffrn_orient_matrix_UB_23      -0.0370124000
_diffrn_orient_matrix_UB_31      0.0243708000
_diffrn_orient_matrix_UB_32      -0.0135099000
_diffrn_orient_matrix_UB_33      -0.0305367000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            59035
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.299
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.231
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.784
_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            'clear bluish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.758
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2524
_exptl_crystal_recrystallization_method 'Slow evaporation from MeCN/MeOH.'
_exptl_crystal_size_max          0.143
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.041
_refine_diff_density_max         2.204
_refine_diff_density_min         -0.781
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         10590
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0663
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0528P)^2^+16.7053P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1131
_refine_ls_wR_factor_ref         0.1196
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8569
_reflns_number_total             10590
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05357a2.cif
_cod_data_source_block           mds322
_cod_depositor_comments
'Adding full bibliography for 1571196--1571204.cif.'
_cod_original_cell_volume        4799.11(19)
_cod_database_code               1571202
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'P1 N4 C20 H20'
_chemical_oxdiff_usercomment     'BpyP=NCN ligand, methanol, Nickel II complex'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1A-C47A = O1B-C47B
 1.427 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(O1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 N9, C48, C49, H49A, H49B, H49C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Br3B)=Sof(O1A)=Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(1)
 Sof(Br3A)=Sof(O1B)=Sof(C47B)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C24(H24), C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32),
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43),
  C44(H44), C45(H45)
6.b Idealised Me refined as rotating group:
 C47A(H47D,H47E,H47F), C47B(H47A,H47B,H47C), C49(H49A,H49B,H49C)
;
_shelx_res_checksum              63222
_olex2_date_sample_data_collection 2023-10-19
_olex2_date_sample_submission    2023-10-19
_olex2_exptl_crystal_mounting_method 'Mounted onto a MiTiGen loop with oil.'
_olex2_submission_original_sample_id mds322
_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 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.609