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_1577037
_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         'C48 H70 Fe Mg N4 O2 P4'
_chemical_formula_sum            'C48 H70 Fe Mg N4 O2 P4'
_chemical_formula_weight         939.12
_chemical_name_systematic        DippBDIMg(iPrN2C)Fp*P4
_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'
_atom_sites_solution_hydrogens   geom
_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                92.7560(10)
_cell_angle_beta                 93.9930(10)
_cell_angle_gamma                94.0270(10)
_cell_formula_units_Z            2
_cell_length_a                   8.99490(10)
_cell_length_b                   14.0741(2)
_cell_length_c                   20.5803(3)
_cell_measurement_reflns_used    33034
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.9070
_cell_measurement_theta_min      3.1320
_cell_volume                     2588.95(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  '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 0.981
_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     78.00 111.00   0.50    0.79    --   79.75-131.00 163.35   66
  2  \w     37.00  72.00   0.50    0.20    --   62.87-147.00  90.00   70
  3  \w     53.00  78.00   0.50    0.79    --   75.95-147.00  90.00   50
  4  \w     80.00 107.00   0.50    0.79    --   75.39-147.00  90.00   54
  5  \w     38.00 108.00   0.50    0.79    --   79.75-127.00 109.79  140
  6  \w     80.00 109.00   0.50    0.79    --   79.75-127.00  40.02   58
  7  \w     83.00 110.00   0.50    0.79    --   79.75-130.00 -10.12   54
  8  \w     50.00  79.00   0.50    0.79    --   79.75-127.00  40.02   58
  9  \w     62.00 109.00   0.50    0.79    --   79.75-127.00 -64.78   94
 10  \w     81.00 109.00   0.50    0.79    --   79.75-127.00-102.20   56
 11  \w     65.00  90.00   0.50    0.79    --   75.95-125.00-103.00   50
 12  \w     49.00  76.00   0.50    0.20    --   62.87-125.00-103.00   54
 13  \w     57.00  94.00   0.50    0.79    --   79.75-128.00-138.61   74
 14  \w     84.00 109.00   0.50    0.79    --   79.75-127.00-143.69   50
 15  \w     56.00  94.00   0.50    0.79    --   79.75-122.00 -84.51   76
 16  \w     49.00  76.00   0.50    0.79    --   79.75-117.00 -61.21   54
 17  \w     40.00  79.00   0.50    0.79    --   79.75-122.00 -17.33   78
 18  \w     25.00  63.00   0.50    0.20    --   62.87 -95.00  90.00   76
 19  \w     44.00  87.00   0.50    0.79    --   79.75-120.00 -42.09   86
 20  \w     43.00  90.00   0.50    0.79    --   79.75-107.00-137.70   94
 21  \w     30.00  57.00   0.50    0.20    --   62.87 -95.00-120.00   54
 22  \w     26.00  51.00   0.50    0.20    --   62.87 -95.00 -90.00   50
 23  \w     26.00  58.00   0.50    0.20    --   62.87 -95.00 -60.00   64
 24  \w     42.00  67.00   0.50    0.79    --   75.95 -95.00 -30.00   50
 25  \w     38.00  63.00   0.50    0.79    --   75.95 -95.00   0.00   50
 26  \w     29.00  56.00   0.50    0.20    --   62.87 -95.00 120.00   54
 27  \w     59.00  84.00   0.50    0.79    --   79.75   4.00  93.66   50
 28  \w     84.00 121.00   0.50    0.79    --   79.75  20.00  36.17   74
 29  \w     89.00 115.00   0.50    0.79    --   79.75  65.00   1.60   52
 30  \w     67.00 100.00   0.50    0.79    --   79.75  21.00  21.93   66
 31  \w     58.00 119.00   0.50    0.79    --   79.75  20.00 -55.85  122
 32  \w     65.00 123.00   0.50    0.79    --   79.75  22.00-139.74  116
 33  \w     83.00 108.00   0.50    0.20    --   62.87  15.00-150.00   50
 34  \w     48.00  94.00   0.50    0.79    --   79.75  15.00-137.00   92
 35  \w     33.00  73.00   0.50    0.20    --   62.87  15.00-150.00   80
 36  \w     48.00 103.00   0.50    0.79    --   79.75  12.00 155.02  110
 37  \w     65.00 116.00   0.50    0.79    --   79.75   6.00 113.58  102
 38  \w     72.00 113.00   0.50    0.79    --   79.75  -2.00   2.41   82
 39  \w     52.00  82.00   0.50    0.79    --   79.75  -4.00-116.37   60
 40  \w     43.00  68.00   0.50    0.79    --   79.75 -69.00  72.88   50
 41  \w     65.00  90.00   0.50    0.79    --   75.39 147.00 139.00   50
 42  \w     73.00 105.00   0.50    0.79    --   75.95 147.00 139.00   64
 43  \w    -76.00 -24.00   0.50    0.20    --  -63.67 147.00 139.00  104
 44  \w   -106.00 -70.00   0.50    0.79    --  -78.25 127.00 140.90   72
 45  \w   -102.00 -77.00   0.50    0.79    --  -76.59 147.00 139.00   50
 46  \w   -115.00 -83.00   0.50    0.20    --  -73.66 147.00 139.00   64
 47  \w   -115.00 -72.00   0.50    0.79    --  -78.25 139.00  83.37   86
 48  \w   -100.00 -34.00   0.50    0.20    --  -73.66 125.00  90.00  132
 49  \w    -80.00 -55.00   0.50    0.20    --  -63.67 125.00 -26.00   50
 50  \w    -93.00 -68.00   0.50    0.79    --  -76.59 125.00 -26.00   50
 51  \w   -100.00 -33.00   0.50    0.20    --  -73.66 125.00 -26.00  134
 52  \w    -93.00 -55.00   0.50    0.20    --  -73.66 125.00 -60.00   76
 53  \w    -99.00 -74.00   0.50    0.20    --  -73.66 125.00 -90.00   50
 54  \w    -57.00 -32.00   0.50    0.20    --  -73.66 125.00 -90.00   50
 55  \w    -89.00 -41.00   0.50    0.79    --  -78.25 118.00  47.07   96
 56  \w    -99.00 -74.00   0.50    0.79    --  -78.25 118.00  66.64   50
 57  \w   -100.00 -75.00   0.50    0.79    --  -78.25 123.00  88.07   50
 58  \w    -87.00 -39.00   0.50    0.79    --  -78.25 118.00 119.58   96
 59  \w    -88.00 -62.00   0.50    0.79    --  -78.25 112.00 -71.76   52
 60  \w    -80.00 -53.00   0.50    0.79    --  -78.25 117.00 -57.09   54
 61  \w    -99.00 -38.00   0.50    0.79    --  -78.25 117.00  -1.46  122
 62  \w    -74.00 -47.00   0.50    0.79    --  -78.25  90.00 111.31   54
 63  \w    -71.00 -44.00   0.50    0.79    --  -78.25  77.00  89.56   54
 64  \w    -72.00 -45.00   0.50    0.79    --  -78.25  75.00  27.24   54
 65  \w    -61.00 -36.00   0.50    0.79    --  -78.25  56.00   3.75   50
 66  \w   -101.00 -37.00   0.50    0.20    --  -63.67   0.00   0.00  128
 67  \w   -113.00 -88.00   0.50    0.79    --  -78.25 -80.00  32.38   50
 68  \w   -120.00 -92.00   0.50    0.79    --  -78.25 -43.00  89.88   56
 69  \w   -116.00 -89.00   0.50    0.79    --  -78.25 -36.00 110.28   54
 70  \w   -114.00 -81.00   0.50    0.79    --  -78.25 -28.00 137.73   66
 71  \w   -108.00 -36.00   0.50    0.20    --  -63.67 -15.00  30.00  144
 72  \w   -119.00 -44.00   0.50    0.20    --  -73.66 -15.00 -90.00  150
 73  \w   -110.00 -70.00   0.50    0.20    --  -73.66-147.00  90.00   80
 74  \w   -112.00 -86.00   0.50    0.79    --  -76.59-147.00  90.00   52
 75  \w   -112.00 -82.00   0.50    0.79    --  -78.25 -85.00  61.30   60
 76  \w   -111.00 -80.00   0.50    0.79    --  -78.25 -81.00 151.08   62
 77  \w   -109.00 -79.00   0.50    0.79    --  -78.25 -91.00  49.68   60
 78  \w   -107.00 -82.00   0.50    0.79    --  -78.25 -83.00 -28.71   50
 79  \w   -112.00 -84.00   0.50    0.79    --  -78.25 -82.00-129.80   56
;
_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      -0.0403893000
_diffrn_orient_matrix_UB_12      -0.1009058000
_diffrn_orient_matrix_UB_13      -0.0314135000
_diffrn_orient_matrix_UB_21      0.0110417000
_diffrn_orient_matrix_UB_22      -0.0414283000
_diffrn_orient_matrix_UB_23      0.0679617000
_diffrn_orient_matrix_UB_31      -0.1669881000
_diffrn_orient_matrix_UB_32      0.0133014000
_diffrn_orient_matrix_UB_33      0.0064151000
_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  0.0384
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            63613
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.320
_diffrn_reflns_theta_min         3.152
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.924
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.618
_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    1.205
_exptl_crystal_description       needle
_exptl_crystal_F_000             1000
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane'
_exptl_crystal_size_max          0.294
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.037
_refine_diff_density_max         0.562
_refine_diff_density_min         -0.454
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     620
_refine_ls_number_reflns         10516
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0374
_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^)+(0.0581P)^2^+0.7540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9497
_reflns_number_total             10516
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg143d_p-1
_cod_database_code               1577037
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C48H70FeMgN4O2P4
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.392
_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
 C00P-C018 \\sim C00P-C0
 with sigma of 0.02
 C018-C01N \\sim C0-C9
 with sigma of 0.02
 C018-C01O \\sim C0-C01P
 with sigma of 0.02
 C00P-C01N \\sim C00P-C9
 with sigma of 0.04
 C00P-C01O \\sim C00P-C01P
 with sigma of 0.04
 C01N-C01O \\sim C9-C01P
 with sigma of 0.04
 C01B-C01H \\sim C01B-C7
 with sigma of 0.02
 C01H-C01L \\sim C7-C8
 with sigma of 0.02
 C01H-C01M \\sim C7-C10
 with sigma of 0.02
 C01B-C01L \\sim C01B-C8
 with sigma of 0.04
 C01B-C01M \\sim C01B-C10
 with sigma of 0.04
 C01L-C01M \\sim C8-C10
 with sigma of 0.04
3. Others
 Sof(C01P)=Sof(H9)=Sof(HQ)=Sof(HR)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C0)=
 Sof(H0)=1-FVAR(1)
 Sof(C018)=Sof(H018)=Sof(C01N)=Sof(H7)=Sof(HM)=Sof(HN)=Sof(C01O)=Sof(H8)=
 Sof(HO)=Sof(HP)=FVAR(1)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C7)=Sof(H7A)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(H8C)=1-FVAR(2)
 Sof(C01H)=Sof(H01)=Sof(C01L)=Sof(H4)=Sof(HI)=Sof(HJ)=Sof(C01M)=Sof(H6)=
 Sof(HK)=Sof(HL)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C00H(H00H), C00J(H00J), C00T(H00T), C018(H018), C01C(H01S), C01H(H01), C0(H0),
  C7(H7A)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C00Y(H00Y), C011(H011), C013(H013), C015(H015), C019(H019), C01D(H01T)
4.c Idealised Me refined as rotating group:
 C00U(H00A,H00B,H00C), C00W(H00D,H00E,H00F), C00X(H00G,H00I,H00K), C010(H01A,
 H01B,H01C), C012(H01D,H01E,H01F), C014(H01G,H01H,H01I), C016(H01J,H01K,H01L),
 C017(H01M,H01N,H01O), C01A(H01P,H01Q,H01R), C01E(H01U,H01V,H01W), C01F(H01X,
 H01Y,H), C01G(H01Z,HA,HB), C01I(H1,HC,HD), C01J(H2,HE,HF), C01K(H3,HG,HH),
 C01L(H4,HI,HJ), C01M(H6,HK,HL), C01N(H7,HM,HN), C01O(H8,HO,HP), C01P(H9,HQ,HR),
  C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              49831
_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 1.267
_oxdiff_exptl_absorpt_empirical_full_min 0.822