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_1577045
_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 O3'
_chemical_formula_sum            'C36 H46 Fe Mg N2 O3'
_chemical_formula_weight         634.928
_chemical_name_systematic        DepBDIMg(THF)Fp
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-28
_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                89.313(2)
_cell_angle_beta                 78.234(2)
_cell_angle_gamma                71.325(2)
_cell_formula_units_Z            2
_cell_length_a                   9.0503(2)
_cell_length_b                   11.8365(2)
_cell_length_c                   16.4701(3)
_cell_measurement_reflns_used    18546
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.2770
_cell_measurement_theta_min      2.7370
_cell_volume                     1633.62(6)
_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  'olex2.refine 1.5 (Bourhis et al., 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 0.9959
_diffrn_measured_fraction_theta_max 0.9791
_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     90.00 115.00   0.50    0.16    --   79.75-139.00-113.92   50
  2  \w     29.00  82.00   0.50    0.16    --   62.61-125.00-120.00  106
  3  \w     43.00  68.00   0.50    0.16    --   75.87-121.00 -58.00   50
  4  \w     29.00  55.00   0.50    0.16    --   62.61-121.00 -58.00   52
  5  \w     48.00  73.00   0.50    0.16    --   79.75-118.00 -56.69   50
  6  \w     77.00 102.00   0.50    0.16    --   79.75-118.00 -56.69   50
  7  \w     27.00  61.00   0.50    0.16    --   62.61 -95.00 -60.00   68
  8  \w     25.00  71.00   0.50    0.16    --   62.61 -95.00   0.00   92
  9  \w     42.00  84.00   0.50    0.16    --   79.75 -98.00 123.88   84
 10  \w     25.00  54.00   0.50    0.16    --   62.61 -95.00 120.00   58
 11  \w     38.00  63.00   0.50    0.16    --   75.87 -95.00 150.00   50
 12  \w     48.00  73.00   0.50    0.16    --   62.61-155.00 143.00   50
 13  \w     81.00 119.00   0.50    0.16    --   75.87-155.00 143.00   76
 14  \w     46.00  71.00   0.50    0.16    --   79.75  -4.00-137.87   50
 15  \w     36.00  61.00   0.50    0.16    --   79.75 -52.00-123.52   50
 16  \w     42.00  67.00   0.50    0.16    --   79.75 -71.00-123.37   50
 17  \w     40.00  65.00   0.50    0.16    --   79.75 -60.00 -85.71   50
 18  \w     43.00  70.00   0.50    0.16    --   79.75  -4.00  32.94   54
 19  \w     41.00  81.00   0.50    0.16    --   79.75  -4.00 148.28   80
 20  \w     64.00  91.00   0.50    0.16    --   75.87 155.00-177.00   54
 21  \w     98.00 125.00   0.50    0.16    --   79.75  22.00 -43.62   54
 22  \w     64.00 103.00   0.50    0.16    --   79.75  21.00-107.92   78
 23  \w     74.00 100.00   0.50    0.16    --   79.75  22.00 -88.68   52
 24  \w     68.00  93.00   0.50    0.16    --   62.61  15.00 -90.00   50
 25  \w     64.00  89.00   0.50    0.16    --   79.75  20.00-126.11   50
 26  \w     32.00  64.00   0.50    0.16    --   62.61  15.00 -90.00   64
 27  \w     82.00 120.00   0.50    0.16    --   79.75  21.00 -64.97   76
 28  \w     76.00 115.00   0.50    0.16    --   79.75  14.00-169.56   78
 29  \w     65.00  90.00   0.50    0.16    --   79.75  22.00  42.67   50
 30  \w     64.00 122.00   0.50    0.16    --   79.75  22.00 119.69  116
 31  \w     53.00 106.00   0.50    0.16    --   62.61  15.00  90.00  106
 32  \w     77.00 123.00   0.50    0.16    --   79.75  13.00  54.82   92
 33  \w     27.00  52.00   0.50    0.16    --   62.61   0.00-150.00   50
 34  \w     54.00 100.00   0.50    0.16    --   62.61   0.00-150.00   92
 35  \w    -82.00 -53.00   0.50    0.16    --  -63.52 155.00-177.00   58
 36  \w   -106.00 -81.00   0.50    0.16    --  -76.46 155.00-177.00   50
 37  \w   -121.00 -94.00   0.50    0.16    --  -73.68 155.00-177.00   54
 38  \w   -113.00 -87.00   0.50    0.16    --  -78.25 137.00-107.27   52
 39  \w   -105.00 -75.00   0.50    0.16    --  -78.25 136.00 -70.22   60
 40  \w    -63.00 -37.00   0.50    0.16    --  -78.25 137.00-107.27   52
 41  \w    -66.00 -38.00   0.50    0.16    --  -78.25 136.00 -70.22   56
 42  \w   -116.00 -80.00   0.50    0.16    --  -78.25 141.00 -23.25   72
 43  \w   -112.00 -85.00   0.50    0.16    --  -78.25 135.00  42.56   54
 44  \w   -110.00 -80.00   0.50    0.16    --  -78.25 132.00  90.95   60
 45  \w   -110.00 -43.00   0.50    0.16    --  -78.25 132.00 172.52  134
 46  \w    -98.00 -34.00   0.50    0.16    --  -73.68 125.00  90.00  128
 47  \w    -66.00 -41.00   0.50    0.16    --  -78.25 132.00  90.95   50
 48  \w    -96.00 -69.00   0.50    0.16    --  -78.25 122.00  48.16   54
 49  \w   -108.00 -69.00   0.50    0.16    --  -78.25 130.00 -39.60   78
 50  \w   -104.00 -77.00   0.50    0.16    --  -78.25 125.00-111.41   54
 51  \w    -95.00 -70.00   0.50    0.16    --  -78.25 121.00-120.48   50
 52  \w    -72.00 -46.00   0.50    0.16    --  -78.25 125.00-111.41   52
 53  \w    -92.00 -67.00   0.50    0.16    --  -76.46 121.00  24.00   50
 54  \w    -95.00 -33.00   0.50    0.16    --  -73.68 121.00  24.00  124
 55  \w    -90.00 -38.00   0.50    0.16    --  -78.25 117.00  -8.11  104
 56  \w    -89.00 -62.00   0.50    0.16    --  -78.25 113.00 -69.69   54
 57  \w    -77.00 -50.00   0.50    0.16    --  -63.52 121.00  24.00   54
 58  \w    -93.00 -62.00   0.50    0.16    --  -78.25 121.00 162.24   62
 59  \w    -90.00 -63.00   0.50    0.16    --  -78.25 119.00 151.23   54
 60  \w    -73.00 -40.00   0.50    0.16    --  -78.25 115.00  46.97   66
 61  \w    -74.00 -44.00   0.50    0.16    --  -78.25  90.00  46.67   60
 62  \w    -77.00 -44.00   0.50    0.16    --  -78.25  86.00  -6.99   66
 63  \w    -88.00 -53.00   0.50    0.16    --  -78.25 102.00-119.65   70
 64  \w   -108.00 -47.00   0.50    0.16    --  -63.52 -15.00-120.00  122
 65  \w   -117.00 -91.00   0.50    0.16    --  -78.25 -44.00  -0.90   52
 66  \w   -111.00 -84.00   0.50    0.16    --  -78.25 -80.00 140.44   54
 67  \w   -112.00 -87.00   0.50    0.16    --  -78.25 -72.00 178.24   50
 68  \w   -110.00 -79.00   0.50    0.16    --  -78.25 -83.00 151.71   62
 69  \w   -107.00 -82.00   0.50    0.16    --  -76.46-155.00 143.00   50
 70  \w    -80.00 -53.00   0.50    0.16    --  -63.52-155.00 143.00   54
 71  \w    -85.00 -50.00   0.50    0.16    --  -78.25-162.00 109.52   70
 72  \w   -110.00 -83.00   0.50    0.16    --  -78.25 -86.00 179.54   54
 73  \w   -112.00 -86.00   0.50    0.16    --  -78.25 -86.00  -9.72   52
 74  \w   -113.00 -83.00   0.50    0.16    --  -78.25 -88.00 -35.96   60
 75  \w   -107.00 -81.00   0.50    0.16    --  -78.25 -83.00-145.03   52
;
_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      0.0820264000
_diffrn_orient_matrix_UB_12      -0.0424873000
_diffrn_orient_matrix_UB_13      -0.0909498000
_diffrn_orient_matrix_UB_21      0.1558968000
_diffrn_orient_matrix_UB_22      -0.0680122000
_diffrn_orient_matrix_UB_23      0.0277043000
_diffrn_orient_matrix_UB_31      -0.0525465000
_diffrn_orient_matrix_UB_32      -0.1118344000
_diffrn_orient_matrix_UB_33      0.0109364000
_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  0.0237
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.9959
_diffrn_reflns_Laue_measured_fraction_max 0.9791
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            32817
_diffrn_reflns_point_group_measured_fraction_full 0.9959
_diffrn_reflns_point_group_measured_fraction_max 0.9791
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         75.10
_diffrn_reflns_theta_min         2.75
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.178
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.659
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             676.296
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.3333
_refine_diff_density_min         -0.2309
_refine_diff_density_rms         0.0490
_refine_ls_d_res_high            0.7977
_refine_ls_d_res_low             16.0974
_refine_ls_goodness_of_fit_ref   1.0238
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    72
_refine_ls_number_parameters     394
_refine_ls_number_reflns         6608
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0238
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0298
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0405P)^2^+0.6528P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0758
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -10
_reflns_limit_k_max              14
_reflns_limit_k_min              -14
_reflns_limit_l_max              20
_reflns_limit_l_min              0
_reflns_number_gt                6164
_reflns_number_total             6608
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           FG105_P1-
_cod_database_code               1577045
_chemical_oxdiff_formula         'C36 H46 Fe Mg N2 O3'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00I(H00b,H00c), C00P(H00i,H00j), C00R(H00m,H00n), C00S(H00o,H00p), C00V(H00r,
 H00s), C00Y(H00v,H00y), C010(H01a,H01b), C012(H01c,H01d)
2.b Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00W(H00W), C00T(H00T), C011(H011), C00L(H00L), C00U(H00U),
 C00Q(H00Q), C00H(H00H), C00X(H00X), C013(H013), C00K(H00K), C00A(H00A)
2.c Idealised Me refined as rotating group:
 C00M(H00d,H00e,H00g), C00Z(H00z,H,Ha), C014(H01e,H01f,H01g), C015(H01h,H01i,
 H01j), C016(H01k,H01l,H01m), C017(H01n,H01o,H01p)
;
_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 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.837