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_1571204
_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_absolute_configuration ad
_chemical_formula_moiety
'0.8(C40 H32 N4 O2 P2), 0.4(H2 O), 1.6(C2 H3 N)'
_chemical_formula_sum            'C35.2 H31.2 N4.8 O2 P1.6'
_chemical_formula_weight         603.00
_chemical_name_common            Compound_31
_chemical_name_systematic        Compound_31
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-04-25 deposited with the CCDC.	2024-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.9480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            5
_cell_length_a                   12.02580(10)
_cell_length_b                   17.46940(10)
_cell_length_c                   19.01960(10)
_cell_measurement_reflns_used    101143
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      77.6400
_cell_measurement_theta_min      3.4360
_cell_volume                     3894.11(5)
_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      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.973
_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      1.00  28.00   0.50    0.05    --   14.00  59.00-129.86   54
  2  \w     11.00  38.00   0.50    0.05    --   22.00  52.00 -98.63   54
  3  \w     15.00  41.00   0.50    0.05    --   26.00  50.00 -18.81   52
  4  \w     15.00  41.00   0.50    0.05    --   26.00  50.00  40.76   52
  5  \w      1.00  28.00   0.50    0.05    --   14.00  59.00  83.61   54
  6  \w     29.00  57.00   0.50    0.05    --   38.00  44.00-146.88   56
  7  \w     68.00 105.00   0.50    0.15    --  107.23 -99.00  30.00   74
  8  \w     59.00 121.00   0.50    0.05    --   50.08-174.00  97.00  124
  9  \w     59.00 146.00   0.50    0.15    --  107.23-174.00  97.00  174
 10  \w     75.00 105.00   0.50    0.15    --  107.23 -99.00  60.00   60
 11  \w     35.00  61.00   0.50    0.15    --  107.23 -99.00  30.00   52
 12  \w     35.00  66.00   0.50    0.15    --  107.23 -99.00 -30.00   62
 13  \w     71.00 105.00   0.50    0.15    --  107.23 -99.00 -30.00   68
 14  \w     27.00  91.00   0.50    0.05    --   50.08-115.00-123.00  128
 15  \w     36.00 101.00   0.50    0.15    --  107.23-125.00-150.00  130
 16  \w     35.00 102.00   0.50    0.15    --  107.23 -99.00-120.00  134
 17  \w     35.00 109.00   0.50    0.15    --  107.23-115.00-123.00  148
 18  \w     36.00 105.00   0.50    0.15    --  107.23 -99.00 -90.00  138
 19  \w     35.00  60.00   0.50    0.15    --  107.23 -99.00  60.00   50
 20  \w     35.00 105.00   0.50    0.15    --  107.23 -99.00 120.00  140
 21  \w     36.00 105.00   0.50    0.15    --  107.23 -99.00 150.00  138
 22  \w     35.00  62.00   0.50    0.15    --  107.23 -57.00  90.00   54
 23  \w     36.00  62.00   0.50    0.15    --  107.23 -57.00 120.00   52
 24  \w     35.00  97.00   0.50    0.15    --  107.23 -77.00  30.00  124
 25  \w     36.00  64.00   0.50    0.15    --  107.23 -57.00  30.00   56
 26  \w     37.00  64.00   0.50    0.15    --  107.23 -57.00 -60.00   54
 27  \w     35.00  60.00   0.50    0.15    --  107.23 -57.00 -90.00   50
 28  \w     38.00  64.00   0.50    0.15    --  107.23 -57.00-120.00   52
 29  \w    100.00 133.00   0.50    0.15    --  107.23  38.00-120.00   66
 30  \w     65.00 122.00   0.50    0.05    --   50.08 174.00 106.00  114
 31  \w     65.00 148.00   0.50    0.15    --  107.23 174.00 106.00  166
 32  \w    101.00 178.00   0.50    0.15    --  107.23 115.00 -33.00  154
 33  \w    144.00 173.00   0.50    0.15    --  107.23  38.00-120.00   58
 34  \w     42.00  67.00   0.50    0.05    --   50.08  41.00 179.18   50
 35  \w    -46.00 -18.00   0.50    0.15    --  -90.00  38.00 -90.00   56
 36  \w    -83.00 -18.00   0.50    0.15    --  -90.00 115.00 -33.00  130
 37  \w   -121.00 -37.00   0.50    0.15    --  -90.00 174.00 106.00  168
 38  \w   -120.00 -45.00   0.50    0.05    --  -50.08 174.00 106.00  150
 39  \w    -83.00  -6.00   0.50    0.05    --  -50.08 115.00 -33.00  154
 40  \w    -45.00 -19.00   0.50    0.15    --  -90.00  38.00 120.00   52
 41  \w   -120.00 -86.00   0.50    0.05    --  -50.00 -42.00   0.26   68
 42  \w    -61.00 -33.00   0.50    0.05    --  -42.00 -43.00-117.74   56
 43  \w    -41.00 -15.00   0.50    0.05    --  -26.00 -50.00 -21.83   52
 44  \w    -21.00   6.00   0.50    0.05    --  -10.00 -65.00 159.53   54
 45  \w    -50.00 -24.00   0.50    0.05    --  -34.00 -46.00 147.62   52
 46  \w    -30.00  -1.00   0.50    0.05    --  -14.00 -57.00  68.36   58
 47  \w    -69.00 -41.00   0.50    0.05    --  -50.00 -42.00  56.50   56
 48  \w    -69.00 -43.00   0.50    0.05    --  -50.00 -42.00  18.26   52
 49  \w    -69.00 -41.00   0.50    0.05    --  -50.00 -42.00   0.26   56
 50  \w    -75.00 -43.00   0.50    0.05    --  -50.00 -42.00  72.78   64
 51  \w   -121.00 -41.00   0.50    0.05    --  -50.00 -42.00 -44.46  160
 52  \w    -75.00 -42.00   0.50    0.05    --  -50.00 -42.00 -64.85   66
 53  \w    -80.00 -43.00   0.50    0.05    --  -50.00 -42.00-145.09   74
 54  \w   -117.00 -83.00   0.50    0.05    --  -50.00 -42.00 -64.85   68
 55  \w   -118.00 -91.00   0.50    0.05    --  -50.00 -42.00 148.88   54
 56  \w    -81.00 -43.00   0.50    0.05    --  -50.00 -42.00 148.88   76
 57  \w    -86.00 -60.00   0.50    0.05    --  -70.00 -42.00 158.23   52
 58  \w    -91.00 -65.00   0.50    0.15    --  -74.00 -42.00 124.36   52
 59  \w    -90.00 -64.00   0.50    0.15    --  -74.00 -42.00  43.29   52
 60  \w    -86.00 -60.00   0.50    0.05    --  -70.00 -42.00  -2.91   52
 61  \w    -90.00 -64.00   0.50    0.15    --  -74.00 -42.00 -59.92   52
 62  \w    -88.00 -62.00   0.50    0.05    --  -70.00 -42.00 -83.75   52
 63  \w    -91.00 -65.00   0.50    0.15    --  -74.00 -42.00-139.86   52
 64  \w    -90.00 -64.00   0.50    0.15    --  -74.00 -42.00-155.32   52
 65  \w    -90.00 -64.00   0.50    0.15    --  -74.00 -42.00-176.19   52
 66  \w    -90.00 -64.00   0.50    0.15    --  -74.00 -42.00-124.59   52
 67  \w    -89.00 -64.00   0.50    0.15    --  -74.00 -42.00-101.68   50
 68  \w    -92.00 -57.00   0.50    0.05    --  -66.00 -41.00 -50.51   70
 69  \w   -138.00-112.00   0.50    0.05    --  -66.00 -41.00 -50.51   52
 70  \w   -118.00 -92.00   0.50    0.05    --  -54.00 -41.00 -31.07   52
 71  \w    -86.00 -61.00   0.50    0.05    --  -70.00 -41.00  51.38   50
 72  \w    -71.00 -45.00   0.50    0.05    --  -54.00 -41.00 -31.07   52
 73  \w    -88.00 -61.00   0.50    0.05    --  -70.00 -41.00  69.75   54
 74  \w    -91.00 -65.00   0.50    0.15    --  -74.00 -41.00 108.55   52
 75  \w    -84.00 -57.00   0.50    0.05    --  -66.00 -41.00 143.74   54
 76  \w    -89.00 -64.00   0.50    0.15    --  -74.00 -42.00 140.61   50
 77  \w    -93.00 -67.00   0.50    0.15    --  -74.00 -41.00 171.65   52
 78  \w   -148.00 -86.00   0.50    0.15    --  -90.00 -42.00 168.58  124
 79  \w   -137.00-109.00   0.50    0.05    --  -66.00 -41.00 143.74   56
 80  \w   -139.00 -82.00   0.50    0.15    --  -90.00 -40.00  39.16  114
 81  \w   -112.00 -81.00   0.50    0.15    --  -90.00 -41.00  70.25   62
 82  \w   -160.00-126.00   0.50    0.15    --  -90.00 -40.00  83.40   68
 83  \w    -99.00 -73.00   0.50    0.15    --  -82.00 -41.00  40.47   52
 84  \w   -119.00 -82.00   0.50    0.15    --  -90.00 -40.00  83.40   74
 85  \w    -94.00 -68.00   0.50    0.15    --  -74.00 -40.00 -11.36   52
 86  \w    -96.00 -70.00   0.50    0.15    --  -78.00 -39.00  21.35   52
 87  \w   -107.00 -81.00   0.50    0.15    --  -90.00 -41.00 -23.65   52
 88  \w   -104.00 -78.00   0.50    0.15    --  -86.00 -39.00 -38.26   52
 89  \w   -160.00-135.00   0.50    0.15    --  -90.00 -39.00 -91.07   50
 90  \w   -155.00-129.00   0.50    0.15    --  -86.00 -39.00 -65.38   52
 91  \w   -104.00 -78.00   0.50    0.15    --  -86.00 -39.00 -65.38   52
 92  \w    -67.00 -42.00   0.50    0.05    --  -50.08 -39.00-178.69   50
 93  \w    -97.00 -71.00   0.50    0.05    --  -50.08 -39.00-178.69   52
 94  \w   -113.00 -82.00   0.50    0.15    --  -90.00 -40.00-156.86   62
 95  \w   -117.00 -82.00   0.50    0.15    --  -90.00 -39.00 -91.07   70
 96  \w   -114.00 -78.00   0.50    0.15    --  -86.00 -39.00  11.52   72
 97  \w   -158.00-132.00   0.50    0.15    --  -90.00 -39.00 106.48   52
 98  \w   -161.00-132.00   0.50    0.15    --  -90.00 -39.00 140.06   58
 99  \w   -118.00 -82.00   0.50    0.15    --  -90.00 -39.00 140.06   72
100  \w   -109.00 -83.00   0.50    0.15    --  -90.00 -39.00 106.48   52
101  \w   -156.00 -78.00   0.50    0.15    --  -86.00 -38.00 -12.01  156
102  \w   -150.00-123.00   0.50    0.15    --  -86.00 -39.00 -38.26   54
103  \w   -109.00 -82.00   0.50    0.15    --  -90.00 -38.00-115.63   54
104  \w   -110.00 -82.00   0.50    0.15    --  -90.00 -38.00-127.87   56
105  \w   -109.00 -83.00   0.50    0.15    --  -90.00 -38.00-141.67   52
106  \w   -160.00-122.00   0.50    0.15    --  -90.00 -38.00-115.63   76
107  \w   -161.00-135.00   0.50    0.15    --  -90.00 -38.00-127.87   52
108  \w   -161.00-136.00   0.50    0.15    --  -90.00 -38.00-141.67   50
109  \w   -122.00 -83.00   0.50    0.15    --  -90.00 -37.00 -73.74   78
110  \w   -103.00 -78.00   0.50    0.15    --  -86.00 -37.00 -22.26   50
111  \w   -147.00-121.00   0.50    0.15    --  -86.00 -37.00 -22.26   52
112  \w   -159.00 -81.00   0.50    0.15    --  -90.00 -36.00 -48.91  156
113  \w   -121.00 -82.00   0.50    0.15    --  -90.00 -36.00  46.74   78
114  \w   -162.00-125.00   0.50    0.15    --  -90.00 -36.00  46.74   74
115  \w   -161.00-111.00   0.50    0.15    --  -90.00 -38.00 120.00  100
116  \w   -107.00 -82.00   0.50    0.15    --  -90.00 -38.00 120.00   50
117  \w   -107.00 -81.00   0.50    0.15    --  -90.00 -36.00  93.63   52
118  \w   -129.00 -81.00   0.50    0.15    --  -90.00 -36.00 168.64   96
119  \w   -122.00 -43.00   0.50    0.05    --  -50.08-174.00  97.00  158
120  \w   -131.00 -43.00   0.50    0.15    --  -90.00-174.00  97.00  176
121  \w   -161.00 -80.00   0.50    0.15    --  -90.00-115.00-123.00  162
122  \w   -161.00-100.00   0.50    0.15    --  -90.00-125.00-150.00  122
;
_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      0.1196784000
_diffrn_orient_matrix_UB_12      -0.0022372000
_diffrn_orient_matrix_UB_13      -0.0165620000
_diffrn_orient_matrix_UB_21      0.0541520000
_diffrn_orient_matrix_UB_22      0.0147942000
_diffrn_orient_matrix_UB_23      0.0802170000
_diffrn_orient_matrix_UB_31      0.0060635000
_diffrn_orient_matrix_UB_32      -0.0868699000
_diffrn_orient_matrix_UB_33      0.0140820000
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            137025
_diffrn_reflns_point_group_measured_fraction_full 0.943
_diffrn_reflns_point_group_measured_fraction_max 0.879
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.600
_diffrn_reflns_theta_min         2.384
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.391
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.393
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       prism
_exptl_crystal_F_000             1580
_exptl_crystal_recrystallization_method
'Slow evaporation from a solution of mds081 in MeCN/H2O'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.627
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 6046 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         14585
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0302
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0496P)^2^+1.2378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0822
_refine_ls_wR_factor_ref         0.0826
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.882
_reflns_Friedel_fraction_max     0.778
_reflns_number_gt                14343
_reflns_number_total             14585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05357a2.cif
_cod_data_source_block           Compound_31
_cod_depositor_comments
'Adding full bibliography for 1571196--1571204.cif.'
_cod_original_formula_sum        'C35.20 H31.20 N4.80 O2 P1.60'
_cod_database_code               1571204
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'N2 P1 O2 C40 H40'
_chemical_oxdiff_usercomment     SWMS-339-54-again-prism
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.680
_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, All O(H,H) groups
2.a Free rotating group:
 O5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C76(H76), C63(H63), C77(H77), C55(H55), C2(H2), C65(H65), C24(H24), C30(H30),
 C36(H36), C44(H44), C43(H43), C40(H40), C11(H11), C38(H38), C25(H25), C8(H8),
 C16(H16), C23(H23), C12(H12), C57(H57), C17(H17), C64(H64), C46(H46), C74(H74),
  C15(H15), C42(H42), C39(H39), C34(H34), C10(H10), C56(H56), C37(H37),
 C80(H80), C45(H45), C9(H9), C70(H70), C78(H78), C6(H6), C79(H79), C50(H50),
 C52(H52), C33(H33), C5(H5), C4(H4), C72(H72), C73(H73), C49(H49), C32(H32),
 C31(H31), C3(H3), C71(H71), C48(H48), C51(H51)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C85(H85A,H85B,H85C), C60(H60A,H60B,H60C), C67(H67A,H67B,
 H67C), C89(H89A,H89B,H89C), C20(H20A,H20B,H20C), C83(H83A,H83B,H83C), C87(H87A,
 H87B,H87C)
;
_shelx_res_checksum              28374
_olex2_exptl_crystal_mounting_method
'mounted onto a MiTiGen loop with paratone oil'
_olex2_submission_original_sample_id mds081
_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 1.144
_oxdiff_exptl_absorpt_empirical_full_min 0.893