Selective White Phosphorus Activation and Functionalization with Inorganic Grignard Reagents
Gilch, Franziska; Brossette, Jan; Westermair, Franz F.; Silva, Wagner; Balázs, Gábor; Gschwind, Ruth M.; Zipse, Hendrik; Wolf, Robert; Chemical Science  (2026) –; doi:10.1039/D6SC01229A

data_1577047
_publ_section_title
;
 Selective White Phosphorus Activation and Functionalization with
 Inorganic Grignard Reagents
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D6SC01229A
_journal_year                    2026
_chemical_formula_moiety         'C40 H56 Fe Mg N2 O P4, 0.5[n-hexane]'
_chemical_formula_sum            'C40 H56 Fe Mg N2 O P4'
_chemical_formula_weight         784.90
_chemical_name_systematic        '[(DippBDI)Mg][Cp*Fe(\h5-P4CO)]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2026-02-05
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-02-09 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   55.0043(4)
_cell_length_b                   24.1155(2)
_cell_length_c                   13.47480(10)
_cell_measurement_reflns_used    28073
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.7780
_cell_measurement_theta_min      3.1990
_cell_volume                     17873.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 43.91a 64-bit (release 29-09-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.36a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_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     35.00  61.00   0.50    1.55    --   60.52 -95.00 -60.00   52
  2  \w     26.00  51.00   0.50    1.55    --   60.52 -95.00-180.00   50
  3  \w     72.00 106.00   0.50    1.55    --   60.52  30.00  30.00   68
  4  \w     11.00  36.00   0.50    1.55    --   60.52 -30.00 150.00   50
  5  \w     14.00  40.00   0.50    1.55    --   60.52 -30.00  30.00   52
  6  \w     12.00  40.00   0.50    1.55    --   60.52 -30.00-120.00   56
  7  \w     45.00  78.00   0.50    1.55    --   74.02 -95.00 -30.00   66
  8  \w    -99.00 -31.00   0.50    1.55    --  -75.11 125.00  90.00  136
  9  \w   -124.00 -77.00   0.50    1.55    --  -75.11 -30.00  60.00   94
 10  \w   -118.00 -88.00   0.50    1.55    --  -75.11-125.00 150.00   60
 11  \w   -120.00 -76.00   0.50    1.55    --  -75.11 -30.00 150.00   88
 12  \w   -109.00 -79.00   0.50    1.55    --  -75.11 -30.00 -60.00   60
 13  \w    -69.00 -31.00   0.50    1.55    --  -75.11 125.00 -30.00   76
 14  \w   -103.00 -78.00   0.50    1.55    --  -75.11 125.00 -30.00   50
 15  \w   -119.00 -76.00   0.50    1.55    --  -75.71-125.00  90.00   86
 16  \w    -95.00 -38.00   0.50    1.55    --  -75.71 125.00-180.00  114
 17  \w     55.00  81.00   0.50    1.55    --   78.50 -95.00  60.00   52
 18  \w     39.00  64.00   0.50    1.55    --   78.50 -95.00 -90.00   50
 19  \w     72.00  97.00   0.50    1.55    --   78.50-125.00-150.00   50
 20  \w     45.00  72.00   0.50    1.55    --   78.50 -95.00 -60.00   54
 21  \w     56.00  82.00   0.50    1.55    --   78.50 -95.00  30.00   52
 22  \w    -67.00 -41.00   0.50    1.55    --  -80.00 111.00  -1.27   52
 23  \w    -99.00 -71.00   0.50    1.55    --  -80.00 111.00  -1.27   56
 24  \w    -91.00 -52.00   0.50    1.55    --  -80.00  95.00-138.81   78
 25  \w   -126.00-101.00   0.50    1.55    --  -80.00 -51.00 124.47   50
 26  \w   -118.00 -92.00   0.50    1.55    --  -80.00 -89.00 -14.37   52
 27  \w   -116.00 -90.00   0.50    1.55    --  -80.00 -34.00  59.45   52
 28  \w   -118.00 -92.00   0.50    1.55    --  -80.00 -46.00 148.25   52
 29  \w   -106.00 -81.00   0.50    1.55    --  -80.00 -86.00  69.18   50
 30  \w    -75.00 -47.00   0.50    1.55    --  -80.00  71.00  -7.76   56
 31  \w   -104.00 -79.00   0.50    1.55    --  -80.00 -90.00  17.73   50
 32  \w   -110.00 -85.00   0.50    1.55    --  -80.00 -89.00 169.99   50
 33  \w    -75.00 -49.00   0.50    1.55    --  -80.00 120.00 165.80   52
 34  \w   -106.00 -81.00   0.50    1.55    --  -80.00 -79.00 133.54   50
 35  \w    -83.00 -41.00   0.50    1.55    --  -80.00 114.00 -37.25   84
 36  \w     50.00 103.00   0.50    1.55    --   82.00-116.00 133.12  106
 37  \w     42.00  73.00   0.50    1.55    --   82.00  -4.00  55.77   62
 38  \w     86.00 112.00   0.50    1.55    --   82.00  22.00  47.31   52
 39  \w     47.00  95.00   0.50    1.55    --   82.00  19.00 -40.54   96
 40  \w     81.00 113.00   0.50    1.55    --   82.00-129.00 122.37   64
 41  \w     79.00 106.00   0.50    1.55    --   82.00-131.00 -44.58   54
 42  \w     53.00  85.00   0.50    1.55    --   82.00   3.00-174.82   64
 43  \w     50.00  79.00   0.50    1.55    --   82.00  15.00-112.99   58
 44  \w     73.00 130.00   0.50    1.55    --   82.00  20.00  92.75  114
 45  \w     42.00  68.00   0.50    1.55    --   82.00-129.00 122.37   52
 46  \w     56.00 113.00   0.50    1.55    --   82.00   6.00 -83.77  114
 47  \w     53.00 131.00   0.50    1.55    --   82.00  20.00   9.33  156
 48  \w     55.00 108.00   0.50    1.55    --   82.00-125.00 -10.70  106
 49  \w     48.00  74.00   0.50    1.55    --   82.00-131.00 -44.58   52
 50  \w     57.00 112.00   0.50    1.55    --   82.00-128.00-125.86  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0198024000
_diffrn_orient_matrix_UB_12      -0.0451697000
_diffrn_orient_matrix_UB_13      0.0017018000
_diffrn_orient_matrix_UB_21      -0.0197739000
_diffrn_orient_matrix_UB_22      0.0451601000
_diffrn_orient_matrix_UB_23      0.0051940000
_diffrn_orient_matrix_UB_31      -0.0011895000
_diffrn_orient_matrix_UB_32      0.0013894000
_diffrn_orient_matrix_UB_33      -0.1141811000
_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  0.0338
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       68
_diffrn_reflns_limit_h_min       -68
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            66638
_diffrn_reflns_point_group_measured_fraction_full 0.846
_diffrn_reflns_point_group_measured_fraction_max 0.830
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.442
_diffrn_reflns_theta_min         3.214
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.423
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.828
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.36a (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 greenish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_description       plate
_exptl_crystal_F_000             6656
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/n-hexane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.256
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 2373 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         7690
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0426
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0645P)^2^+39.4221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1124
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.607
_reflns_Friedel_fraction_full    0.679
_reflns_Friedel_fraction_max     0.656
_reflns_number_gt                7035
_reflns_number_total             7690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg123c_fdd2
_cod_database_code               1577047
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H56FeMgN2OP4
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.472
_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.a Ternary CH refined with riding coordinates:
 C00N(H00N), C00P(H00P), C00U(H00U), C00Y(H00Y)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C00G(H00G), C00H(H00H), C00I(H00I), C00W(H00W), C014(H014), C016(H016)
2.c Idealised Me refined as rotating group:
 C00S(H00a,H00b,H00c), C00T(H00d,H00e,H00f), C00X(H00j,H00k,H00l), C010(H01a,
 H01b,H01c), C011(H01d,H01e,H01f), C012(H01g,H01h,H01i), C013(H01j,H01k,H01l),
 C015(H01m,H01n,H01o), C017(H01p,H01q,H01r), C018(H01s,H01t,H01u), C019(H01v,
 H01w,H01x), C01A(H01y,H,Ha), C01B(H01z,Hb,Hc), C01C(H01,Hd,He), C01D(H1,Hf,Hg)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              37528
_shelx_fab_checksum              83622
_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 2.668
_oxdiff_exptl_absorpt_empirical_full_min 0.632