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_1577043
_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         'C36 H46 Fe Mg N2 O2 P4, 0.5[C7H8]'
_chemical_formula_sum            'C39.5 H50 Fe Mg N2 O2 P4'
_chemical_formula_weight         788.85
_chemical_name_systematic        DippBDIMgFpP4
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-02-09 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8960(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   42.1585(5)
_cell_length_b                   11.94440(10)
_cell_length_c                   16.16690(10)
_cell_measurement_reflns_used    26726
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.6830
_cell_measurement_theta_min      2.7100
_cell_volume                     8130.57(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 43.131a 64-bit (release 19-07-2024))'
_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 0.999
_diffrn_measured_fraction_theta_max 0.982
_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     47.00  72.00   0.50    3.22    --   62.96-154.00 -26.00   50
  2  \w     30.00  55.00   0.50    3.22    --   62.96-121.00 131.00   50
  3  \w    -80.00 -54.00   0.50    3.22    --  -63.83-154.00 -26.00   52
  4  \w    -75.00 -35.00   0.50    3.22    --  -63.83 121.00-145.00   80
  5  \w   -102.00 -75.00   0.50    3.22    --  -73.70-154.00 -26.00   54
  6  \w    -98.00 -69.00   0.50    3.22    --  -73.70 121.00-145.00   58
  7  \w     56.00  81.00   0.50    3.22    --   75.50-154.00 -26.00   50
  8  \w     62.00  87.00   0.50    3.22    --   75.50 154.00  12.00   50
  9  \w     56.00  81.00   0.50    3.22    --   75.94-154.00 -26.00   50
 10  \w     43.00  68.00   0.50    3.22    --   75.94-121.00 131.00   50
 11  \w    -92.00 -67.00   0.50    3.22    --  -76.64 121.00-145.00   50
 12  \w   -105.00 -80.00   0.50    3.22    --  -76.64 154.00  12.00   50
 13  \w   -108.00 -83.00   0.50    3.22    --  -76.64-154.00 -26.00   50
 14  \w     35.00 108.00   0.50    3.22    --   62.96  15.00  30.00  146
 15  \w     34.00 107.00   0.50    3.22    --   62.96  15.00 -90.00  146
 16  \w     28.00  70.00   0.50    3.22    --   62.96 -95.00 -30.00   84
 17  \w     26.00  69.00   0.50    3.22    --   62.96 -95.00  60.00   86
 18  \w     33.00  65.00   0.50    3.22    --   62.96 -95.00-150.00   64
 19  \w     38.00  63.00   0.50    3.22    --   75.94 -95.00 -30.00   50
 20  \w   -109.00 -74.00   0.50    3.22    --  -78.25 130.00 161.42   70
 21  \w    -75.00 -49.00   0.50    3.22    --  -78.25 125.00 121.40   52
 22  \w    -62.00 -37.00   0.50    3.22    --  -78.25  57.00-109.02   50
 23  \w   -118.00 -58.00   0.50    3.22    --  -78.25 144.00-136.56  120
 24  \w   -108.00 -58.00   0.50    3.22    --  -78.25 134.00-142.11  100
 25  \w   -116.00 -41.00   0.50    3.22    --  -78.25 141.00 178.90  150
 26  \w    -82.00 -45.00   0.50    3.22    --  -78.25  98.00 -58.07   74
 27  \w    -99.00 -45.00   0.50    3.22    --  -78.25 115.00 -62.96  108
 28  \w    -83.00 -45.00   0.50    3.22    --  -78.25  89.00-171.75   76
 29  \w    -64.00 -39.00   0.50    3.22    --  -78.25  61.00-134.14   50
 30  \w     44.00  84.00   0.50    3.22    --   79.75  -2.00 -23.76   80
 31  \w     57.00  98.00   0.50    3.22    --   79.75   1.00  96.83   82
 32  \w     71.00 126.00   0.50    3.22    --   79.75  22.00  46.78  110
 33  \w     75.00 122.00   0.50    3.22    --   79.75  23.00 -32.91   94
 34  \w     71.00 127.00   0.50    3.22    --   79.75  22.00 -67.85  112
 35  \w     70.00 126.00   0.50    3.22    --   79.75  21.00  18.62  112
 36  \w     61.00 120.00   0.50    3.22    --   79.75  21.00-101.03  118
 37  \w     90.00 115.00   0.50    3.22    --   79.75  -2.00 -23.76   50
 38  \w     43.00  83.00   0.50    3.22    --   79.75  -4.00-138.78   80
;
_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      -0.0360359000
_diffrn_orient_matrix_UB_12      -0.0148145000
_diffrn_orient_matrix_UB_13      -0.0169322000
_diffrn_orient_matrix_UB_21      0.0047374000
_diffrn_orient_matrix_UB_22      -0.1269985000
_diffrn_orient_matrix_UB_23      -0.0106013000
_diffrn_orient_matrix_UB_31      -0.0041311000
_diffrn_orient_matrix_UB_32      -0.0170954000
_diffrn_orient_matrix_UB_33      0.0933048000
_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  0.0402
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -51
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            51258
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.080
_diffrn_reflns_theta_min         3.847
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.887
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.36a (Rigaku Oxford Diffraction, 2022)
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    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             3320
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.668
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     425
_refine_ls_number_reflns         8243
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0604P)^2^+5.8378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1058
_refine_ls_wR_factor_ref         0.1086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7273
_reflns_number_total             8243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg160_red
_cod_original_formula_sum        'C39.50 H50 Fe Mg N2 O2 P4'
_cod_database_code               1577043
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C39H48FeMgN2O2P4
_shelx_estimated_absorpt_t_max   0.758
_shelx_estimated_absorpt_t_min   0.569
_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:
 C00K(H00K), C00L(H00L), C00U(H00U), C00V(H00V)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C00M(H00M), C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R),
 C00S(H00S), C00W(H00W), C010(H010), C012(H012), C013(H013), C015(H015)
2.c Idealised Me refined as rotating group:
 C00P(H00A,H00B,H00C), C00T(H00D,H00E,H00F), C00X(H00G,H00H,H00I), C011(H01A,
 H01B,H01C), C014(H01D,H01E,H01F), C016(H01G,H01H,H01I), C017(H01J,H01K,H01L),
 C018(H01M,H01N,H01O), C019(H01P,H01Q,H01R), C01A(H01S,H01T,H01U)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              37408
_shelx_fab_checksum              81304
_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 4.820
_oxdiff_exptl_absorpt_empirical_full_min 0.203