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_1577049
_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         'C39 H54 Fe Mg N2 O2 P4, 0.5[C7H8]'
_chemical_formula_sum            'C42.5 H58 Fe Mg N2 O2 P4'
_chemical_formula_weight         832.95
_chemical_name_systematic        '[(DippBDI)Mg(THF)][CpFe(\h5-P4CO)]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2026-02-09
_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                 97.0340(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.66380(10)
_cell_length_b                   14.16700(10)
_cell_length_c                   16.45870(10)
_cell_measurement_reflns_used    40816
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.6220
_cell_measurement_theta_min      2.3660
_cell_volume                     4319.09(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 42.92a 64-bit (release 29-05-2023))'
_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 1.000
_diffrn_measured_fraction_theta_max 0.986
_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     24.00  72.00   0.50    0.81    --   62.92-100.00-132.00   96
  2  \w    -53.00 -27.00   0.50    0.81    --  -63.82 100.00 -27.00   52
  3  \w    -84.00 -59.00   0.50    0.81    --  -73.68 100.00 -27.00   50
  4  \w     39.00  82.00   0.50    0.81    --   75.87-100.00-132.00   86
  5  \w    -87.00 -62.00   0.50    0.81    --  -76.65 100.00 -27.00   50
  6  \w    -63.00 -38.00   0.50    0.81    --  -26.00 -71.00 -14.58   50
  7  \w     36.00  62.00   0.50    0.81    --   30.00  72.00 -55.13   52
  8  \w     48.00  73.00   0.50    0.81    --   42.00  72.00 -35.15   50
  9  \w     58.00  83.00   0.50    0.81    --   50.00  68.00 -19.23   50
 10  \w     57.00  82.00   0.50    0.81    --   50.00  71.00 -10.16   50
 11  \w     61.00  86.00   0.50    0.81    --   54.00  71.00   2.72   50
 12  \w     67.00  92.00   0.50    0.81    --   58.00  64.00 -32.98   50
 13  \w     64.00  89.00   0.50    0.81    --   58.00  72.00  14.16   50
 14  \w     68.00  98.00   0.50    0.81    --   62.00  72.00  18.36   60
 15  \w     65.00  96.00   0.50    0.81    --   62.92   0.00  60.00   62
 16  \w     27.00  60.00   0.50    0.81    --   62.92   0.00  60.00   66
 17  \w     24.00  70.00   0.50    0.81    --   62.92-125.00 -60.00   92
 18  \w     28.00  63.00   0.50    0.81    --   62.92 -95.00 -30.00   70
 19  \w     32.00  69.00   0.50    0.81    --   62.92  15.00-180.00   74
 20  \w     46.00  71.00   0.50    0.81    --   62.92 -95.00  60.00   50
 21  \w    -88.00 -58.00   0.50    0.81    --  -63.82 125.00  60.00   60
 22  \w    -90.00 -22.00   0.50    0.81    --  -63.82 125.00  90.00  136
 23  \w    -53.00 -27.00   0.50    0.81    --  -63.82 125.00  60.00   52
 24  \w   -101.00 -75.00   0.50    0.81    --  -70.00 -74.00 -23.88   52
 25  \w   -108.00 -79.00   0.50    0.81    --  -70.00 -64.00-112.26   58
 26  \w    -69.00 -36.00   0.50    0.81    --  -73.68   0.00 -30.00   66
 27  \w   -110.00 -74.00   0.50    0.81    --  -73.68   0.00 -30.00   72
 28  \w   -114.00 -82.00   0.50    0.81    --  -74.00 -65.00 -70.64   64
 29  \w   -110.00 -78.00   0.50    0.81    --  -74.00 -75.00 -39.93   64
 30  \w   -106.00 -80.00   0.50    0.81    --  -78.00 -78.00 -47.64   52
 31  \w   -105.00 -80.00   0.50    0.81    --  -78.00 -78.00 -16.75   50
 32  \w   -108.00 -79.00   0.50    0.81    --  -78.25 -81.00 -37.99   58
 33  \w    -78.00 -46.00   0.50    0.81    --  -78.25  98.00 -93.25   64
 34  \w   -107.00 -81.00   0.50    0.81    --  -78.25 -83.00 126.65   52
 35  \w   -104.00 -79.00   0.50    0.81    --  -78.25 -84.00  33.62   50
 36  \w   -104.00 -79.00   0.50    0.81    --  -78.25 -84.00   5.67   50
 37  \w   -111.00 -85.00   0.50    0.81    --  -78.25 -80.00 179.16   52
 38  \w    -76.00 -40.00   0.50    0.81    --  -78.25 123.00 -66.86   72
 39  \w   -108.00 -81.00   0.50    0.81    --  -78.25 -77.00 145.50   54
 40  \w   -116.00 -91.00   0.50    0.81    --  -78.25 -70.00  28.38   50
 41  \w   -106.00 -80.00   0.50    0.81    --  -78.25 -85.00 -78.86   52
 42  \w    -61.00 -36.00   0.50    0.81    --  -78.25 121.00-108.89   50
 43  \w   -110.00 -84.00   0.50    0.81    --  -78.25 -72.00  10.29   52
 44  \w    -96.00 -70.00   0.50    0.81    --  -78.25 121.00-108.89   52
 45  \w    -73.00 -48.00   0.50    0.81    --  -78.25 111.00 -44.78   50
 46  \w   -113.00 -87.00   0.50    0.81    --  -78.25 -83.00-163.55   52
 47  \w   -105.00 -80.00   0.50    0.81    --  -78.25 -79.00   6.49   50
 48  \w    -68.00 -39.00   0.50    0.81    --  -78.25 113.00-118.12   58
 49  \w    -97.00 -72.00   0.50    0.81    --  -78.25 113.00-118.12   50
 50  \w    -90.00 -39.00   0.50    0.81    --  -78.25 102.00-127.24  102
 51  \w   -112.00 -80.00   0.50    0.81    --  -78.25 -79.00 -64.10   64
 52  \w    -79.00 -44.00   0.50    0.81    --  -78.25 113.00 -94.45   70
 53  \w   -104.00 -44.00   0.50    0.81    --  -78.25-172.00 -54.55  120
 54  \w   -105.00 -79.00   0.50    0.81    --  -78.25 -85.00 -64.00   52
 55  \w   -113.00 -81.00   0.50    0.81    --  -78.25 -78.00 -20.70   64
 56  \w    -99.00 -59.00   0.50    0.81    --  -78.25 119.00-173.47   80
 57  \w     40.00  81.00   0.50    0.81    --   79.75  -4.00-170.64   82
 58  \w     96.00 123.00   0.50    0.81    --   79.75  10.00 -66.04   54
 59  \w     39.00  95.00   0.50    0.81    --   79.75-119.00   8.75  112
 60  \w     65.00  93.00   0.50    0.81    --   79.75  10.00 -66.04   56
 61  \w     41.00 116.00   0.50    0.81    --   79.75  -2.00  67.12  150
 62  \w     61.00 103.00   0.50    0.81    --   79.75  20.00-126.61   84
 63  \w     63.00 112.00   0.50    0.81    --   79.75   5.00-179.08   98
 64  \w     71.00 127.00   0.50    0.81    --   79.75  22.00 162.97  112
 65  \w     88.00 113.00   0.50    0.81    --   79.75  67.00 162.03   50
 66  \w     56.00 118.00   0.50    0.81    --   79.75  16.00  29.53  124
 67  \w     40.00  80.00   0.50    0.81    --   79.75  -4.00  23.99   80
 68  \w     47.00  80.00   0.50    0.81    --   79.75  -4.00 145.32   66
 69  \w     93.00 118.00   0.50    0.81    --   79.75  35.00 -80.09   50
 70  \w     43.00 116.00   0.50    0.81    --   79.75   1.00-110.14  146
 71  \w     72.00 126.00   0.50    0.81    --   79.75  24.00  54.44  108
 72  \w     54.00 107.00   0.50    0.81    --   79.75  15.00  -1.95  106
;
_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      -0.0135262000
_diffrn_orient_matrix_UB_12      -0.0474216000
_diffrn_orient_matrix_UB_13      -0.0846975000
_diffrn_orient_matrix_UB_21      0.0778681000
_diffrn_orient_matrix_UB_22      0.0233097000
_diffrn_orient_matrix_UB_23      -0.0152200000
_diffrn_orient_matrix_UB_31      0.0259129000
_diffrn_orient_matrix_UB_32      -0.0950322000
_diffrn_orient_matrix_UB_33      0.0385969000
_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  0.0330
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            92304
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.382
_diffrn_reflns_theta_min         2.385
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.625
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.750
_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            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_description       block
_exptl_crystal_F_000             1764
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.594
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     717
_refine_ls_number_reflns         8829
_refine_ls_number_restraints     408
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0356
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0568P)^2^+1.5710P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1009
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7882
_reflns_number_total             8829
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg78_p21_c
_cod_original_formula_sum        'C42.50 H58 Fe Mg N2 O2 P4'
_cod_database_code               1577049
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C42 H56 Fe Mg N2 O2 P4'
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.544
_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
 C8-C9 \\sim C8-C9A
 with sigma of 0.02
 C9-C11 \\sim C9A-C11A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C8-C11 \\sim C8-C11A
 with sigma of 0.04
 C8-C10 \\sim C8-C10A
 with sigma of 0.04
 C11-C10 \\sim C11A-C10A
 with sigma of 0.04
 C20-C21 \\sim C20-C21A
 with sigma of 0.02
 C21-C23 \\sim C21A-C23A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C20-C23 \\sim C20-C23A
 with sigma of 0.04
 C20-C22 \\sim C20-C22A
 with sigma of 0.04
 C23-C22 \\sim C23A-C22A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Others
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=1-FVAR(1)
 Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C21A)=Sof(H21A)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(2)
 Sof(C21)=Sof(H21)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C9A(H9A), C21A(H21A)
5.b Me refined with riding coordinates:
 C22A(H22D,H22E,H22F)
5.c Idealised Me refined as rotating group:
 C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C23A(H23D,H23E,H23F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 96 electrons were 
found in a volume of 440\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.5[C7H8] per Asymmetric Unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84590
_shelx_fab_checksum              31128
_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 1.506
_oxdiff_exptl_absorpt_empirical_full_min 0.721