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_1577044
_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         'C41 H56 Fe Mg N2 O2 P4'
_chemical_formula_sum            'C41 H56 Fe Mg N2 O2 P4'
_chemical_formula_weight         812.91
_chemical_name_systematic        DippBDIMgFp*P4
_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   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                 104.0650(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.57960(10)
_cell_length_b                   15.17910(10)
_cell_length_c                   23.6402(2)
_cell_measurement_reflns_used    36529
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      72.8750
_cell_measurement_theta_min      3.4710
_cell_volume                     4378.70(6)
_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  (Sheldrick, 2015)'
_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 0.978
_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     54.00  80.00   0.50    0.88    --   62.92-153.00  43.00   52
  2  \w     53.00  78.00   0.50    0.88    --   73.03-153.00  43.00   50
  3  \w     55.00  80.00   0.50    0.88    --   75.56-153.00  43.00   50
  4  \w     37.00  96.00   0.50    0.88    --   75.56-125.00  60.00  118
  5  \w     25.00  89.00   0.50    0.88    --   62.92-125.00 -30.00  128
  6  \w     34.00 102.00   0.50    0.88    --   75.56-125.00 -90.00  136
  7  \w     39.00  84.00   0.50    0.88    --   75.56-125.00-120.00   90
  8  \w     39.00  65.00   0.50    0.88    --   75.56-121.00-157.00   52
  9  \w     40.00  65.00   0.50    0.88    --   73.03-121.00-157.00   50
 10  \w     25.00  67.00   0.50    0.88    --   62.92 -95.00-120.00   84
 11  \w     23.00  81.00   0.50    0.88    --   62.92-121.00-157.00  116
 12  \w     34.00 101.00   0.50    0.88    --   75.56-125.00 -30.00  134
 13  \w     25.00  71.00   0.50    0.88    --   62.92 -95.00  30.00   92
 14  \w     37.00 102.00   0.50    0.88    --   75.56-125.00  90.00  130
 15  \w     25.00  58.00   0.50    0.88    --   62.92 -95.00 120.00   66
 16  \w     25.00  70.00   0.50    0.88    --   62.92 -95.00  90.00   90
 17  \w     26.00 100.00   0.50    0.88    --   62.92   0.00 120.00  148
 18  \w     49.00 104.00   0.50    0.88    --   75.56  15.00  90.00  110
 19  \w     61.00  86.00   0.50    0.88    --   73.03 153.00  83.00   50
 20  \w     68.00 110.00   0.50    0.88    --   75.56 153.00  83.00   84
 21  \w     38.00 112.00   0.50    0.88    --   75.56   0.00-180.00  148
 22  \w   -101.00 -26.00   0.50    0.88    --  -63.82   0.00-150.00  150
 23  \w    -69.00 -35.00   0.50    0.88    --  -63.82 153.00  83.00   68
 24  \w   -107.00 -74.00   0.50    0.88    --  -63.82 153.00  83.00   66
 25  \w   -119.00 -91.00   0.50    0.88    --  -73.46 153.00  83.00   56
 26  \w   -122.00 -96.00   0.50    0.88    --  -76.65 153.00  83.00   52
 27  \w    -91.00 -39.00   0.50    0.88    --  -76.65 153.00  83.00  104
 28  \w   -103.00 -37.00   0.50    0.88    --  -76.65 125.00  60.00  132
 29  \w    -88.00 -27.00   0.50    0.88    --  -63.82 121.00 -75.00  122
 30  \w    -97.00 -48.00   0.50    0.88    --  -73.46 121.00 -75.00   98
 31  \w   -101.00 -58.00   0.50    0.88    --  -76.65 121.00 -75.00   86
 32  \w   -103.00 -39.00   0.50    0.88    --  -76.65 125.00-150.00  128
 33  \w   -109.00 -33.00   0.50    0.88    --  -63.82 -15.00 -60.00  152
 34  \w   -114.00 -73.00   0.50    0.88    --  -76.65-125.00 -90.00   82
 35  \w    -79.00 -54.00   0.50    0.88    --  -63.82-153.00  43.00   50
 36  \w    -98.00 -72.00   0.50    0.88    --  -73.46-153.00  43.00   52
 37  \w   -108.00 -83.00   0.50    0.88    --  -76.65-153.00  43.00   50
 38  \w   -118.00 -73.00   0.50    0.88    --  -76.65-125.00  60.00   90
 39  \w   -115.00 -85.00   0.50    0.88    --  -76.65-125.00 -30.00   60
 40  \w   -118.00 -81.00   0.50    0.88    --  -76.65-125.00 -60.00   74
 41  \w   -115.00 -73.00   0.50    0.88    --  -76.65-125.00-120.00   84
;
_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      0.0395667000
_diffrn_orient_matrix_UB_12      0.0447394000
_diffrn_orient_matrix_UB_13      0.0599440000
_diffrn_orient_matrix_UB_21      -0.0050349000
_diffrn_orient_matrix_UB_22      0.0904278000
_diffrn_orient_matrix_UB_23      -0.0301487000
_diffrn_orient_matrix_UB_31      -0.1197261000
_diffrn_orient_matrix_UB_32      0.0109934000
_diffrn_orient_matrix_UB_33      0.0038756000
_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  0.0503
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            70904
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.199
_diffrn_reflns_theta_min         3.492
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.550
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.758
_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 orangish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       needle
_exptl_crystal_F_000             1720
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene/n-hexane'
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.279
_refine_diff_density_min         -0.649
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         8585
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0817P)^2^+2.7622P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1263
_refine_ls_wR_factor_ref         0.1289
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7795
_reflns_number_total             8585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           dippmgfec5me5_p21-c
_cod_database_code               1577044
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C, H, N, Mg, Fe, O, P'
_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. Rigid bond restraints
 P2, P1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3.a Ternary CH refined with riding coordinates:
 C00G(H00G), C00P(H00P), C00U(H00U), C00V(H00V)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C00O(H00O), C00Q(H00Q), C00R(H00R), C016(H016), C017(H017), C01E(H1)
3.c Idealised Me refined as rotating group:
 C00M(H00A,H00B,H00C), C00N(H00D,H00E,H00F), C00X(H00H,H00I,H00J), C010(H01A,
 H01B,H01C), C012(H01D,H01E,H01F), C013(H01G,H01H,H01I), C014(H01J,H01K,H01L),
 C015(H01M,H01N,H01O), C018(H01P,H01Q,H01R), C019(H01S,H01T,H01U), C01A(H01V,
 H01W,H01X), C01B(H01Y,H,HA), C01C(H01Z,HB,HC), C01D(H01,HD,HE), C01F(H2,HF,HG)
;
_shelx_res_checksum              94428
_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 1.495
_oxdiff_exptl_absorpt_empirical_full_min 0.768