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_1577046
_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         'C7 H5 Fe O2, C43 H60 Mg N6, 0.5(C4 H8 O)'
_chemical_formula_sum            'C52 H69 Fe Mg N6 O2.5'
_chemical_formula_weight         898.29
_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             2026-03-23
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-03-25 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.7200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.9332(2)
_cell_length_b                   9.51240(10)
_cell_length_c                   28.1357(3)
_cell_measurement_reflns_used    48703
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.3270
_cell_measurement_theta_min      3.1900
_cell_volume                     5203.95(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 44.142a 64-bit (release 06-02-2026))'
_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 0.999
_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     26.00  59.00   0.50    3.14    --   63.33 -95.00  30.00   66
  2  \w     27.00  60.00   0.50    3.14    --   63.33 -95.00 150.00   66
  3  \w     35.00 109.00   0.50    3.14    --   63.33  15.00 120.00  148
  4  \w     61.00 106.00   0.50    3.14    --   63.33  15.00-150.00   90
  5  \w     37.00  63.00   0.50    3.14    --   63.33 -95.00 -90.00   52
  6  \w     57.00  84.00   0.50    3.14    --   63.33-125.00 -60.00   54
  7  \w     23.00  50.00   0.50    3.14    --   63.33-125.00 -60.00   54
  8  \w     26.00  90.00   0.50    3.14    --   63.33-125.00 120.00  128
  9  \w     27.00  71.00   0.50    3.14    --   63.33 -95.00-180.00   88
 10  \w    -90.00 -64.00   0.50    3.14    --  -63.85 125.00 120.00   52
 11  \w    -55.00 -21.00   0.50    3.14    --  -63.85 125.00 120.00   68
 12  \w   -101.00 -57.00   0.50    3.14    --  -63.85 -15.00 -60.00   88
 13  \w    -78.00 -27.00   0.50    3.14    --  -63.85 125.00 -90.00  102
 14  \w    -64.00 -38.00   0.50    3.14    --  -63.85 125.00  60.00   52
 15  \w   -108.00 -83.00   0.50    3.14    --  -63.85 -15.00-150.00   50
 16  \w    -78.00 -39.00   0.50    3.14    --  -63.85 -15.00-150.00   78
 17  \w    -62.00 -37.00   0.50    3.14    --  -73.74 125.00   0.00   50
 18  \w   -104.00 -73.00   0.50    3.14    --  -73.74-125.00-180.00   62
 19  \w   -101.00 -64.00   0.50    3.14    --  -73.74 125.00 -60.00   74
 20  \w    -72.00 -45.00   0.50    3.14    --  -73.74 -15.00-180.00   54
 21  \w   -118.00 -84.00   0.50    3.14    --  -73.74 -15.00-180.00   68
 22  \w   -101.00 -75.00   0.50    3.14    --  -73.74 125.00-180.00   52
 23  \w    -59.00 -33.00   0.50    3.14    --  -73.74 125.00 -60.00   52
 24  \w   -102.00 -76.00   0.50    3.14    --  -73.74 125.00  90.00   52
 25  \w    -64.00 -32.00   0.50    3.14    --  -73.74 125.00-180.00   64
 26  \w     38.00  63.00   0.50    3.14    --   75.69 -95.00-150.00   50
 27  \w   -103.00 -75.00   0.50    3.14    --  -78.25 119.00  30.78   56
 28  \w   -102.00 -53.00   0.50    3.14    --  -78.25 116.00 -65.47   98
 29  \w   -120.00 -94.00   0.50    3.14    --  -78.25 -41.00  46.46   52
 30  \w    -60.00 -34.00   0.50    3.14    --  -78.25 119.00  30.78   52
 31  \w    -67.00 -40.00   0.50    3.14    --  -78.25  67.00 -34.29   54
 32  \w   -110.00 -85.00   0.50    3.14    --  -78.25 -81.00  82.10   50
 33  \w   -107.00 -81.00   0.50    3.14    --  -78.25 125.00 168.50   52
 34  \w    -70.00 -45.00   0.50    3.14    --  -78.25-163.00 -37.78   50
 35  \w   -110.00 -85.00   0.50    3.14    --  -78.25 -83.00 -97.63   50
 36  \w    -90.00 -47.00   0.50    3.14    --  -78.25-163.00 -41.23   86
 37  \w    -90.00 -47.00   0.50    3.14    --  -78.25 132.00 -53.01   86
 38  \w   -108.00 -58.00   0.50    3.14    --  -78.25 127.00 -88.04  100
 39  \w   -113.00 -88.00   0.50    3.14    --  -78.25 -82.00  18.61   50
 40  \w    -77.00 -52.00   0.50    3.14    --  -78.25  97.00  23.44   50
 41  \w    -74.00 -42.00   0.50    3.14    --  -78.25  88.00  61.70   64
 42  \w   -112.00 -86.00   0.50    3.14    --  -78.25 -89.00  14.47   52
 43  \w   -102.00 -76.00   0.50    3.14    --  -78.25 -88.00  26.78   52
 44  \w   -105.00 -79.00   0.50    3.14    --  -78.25 -90.00  69.25   52
 45  \w   -103.00 -63.00   0.50    3.14    --  -78.25 117.00-156.69   80
 46  \w   -107.00 -57.00   0.50    3.14    --  -78.25 125.00-147.89  100
 47  \w    -68.00 -36.00   0.50    3.14    --  -78.25 115.00  17.74   64
 48  \w    -82.00 -56.00   0.50    3.14    --  -78.25 112.00-140.90   52
 49  \w    -70.00 -45.00   0.50    3.14    --  -78.25  66.00-109.69   50
 50  \w    -80.00 -54.00   0.50    3.14    --  -78.25 113.00  86.52   52
 51  \w   -108.00 -80.00   0.50    3.14    --  -78.25 -91.00 118.08   56
 52  \w   -104.00 -77.00   0.50    3.14    --  -78.25 -84.00 -65.35   54
 53  \w   -122.00 -97.00   0.50    3.14    --  -78.25 -42.00-123.60   50
 54  \w    -60.00 -35.00   0.50    3.14    --  -78.25 114.00  13.82   50
 55  \w    -96.00 -64.00   0.50    3.14    --  -78.25 118.00  50.74   64
 56  \w     63.00  96.00   0.50    3.14    --   79.75  20.00 -25.76   66
 57  \w     46.00  90.00   0.50    3.14    --   79.75   6.00 108.67   88
 58  \w     41.00  94.00   0.50    3.14    --   79.75-125.00 -12.62  106
 59  \w     65.00  92.00   0.50    3.14    --   79.75  21.00 108.75   54
 60  \w     45.00 119.00   0.50    3.14    --   79.75   5.00   5.59  148
 61  \w     86.00 122.00   0.50    3.14    --   79.75  21.00 172.43   72
 62  \w     52.00 108.00   0.50    3.14    --   79.75-125.00  35.93  112
 63  \w     47.00 118.00   0.50    3.14    --   79.75   2.00-176.38  142
 64  \w     46.00 106.00   0.50    3.14    --   79.75-121.00  63.46  120
 65  \w     61.00 111.00   0.50    3.14    --   79.75  21.00-135.86  100
 66  \w     74.00 109.00   0.50    3.14    --   79.75-127.00-129.96   70
 67  \w     71.00  98.00   0.50    3.14    --   79.75  21.00  35.27   54
 68  \w    101.00 126.00   0.50    3.14    --   79.75  20.00 162.17   50
 69  \w     67.00 122.00   0.50    3.14    --   79.75  23.00 131.72  110
 70  \w     49.00 101.00   0.50    3.14    --   79.75-115.00-167.59  104
 71  \w     73.00 100.00   0.50    3.14    --   79.75  22.00 -85.73   54
 72  \w     63.00 105.00   0.50    3.14    --   79.75  19.00  22.93   84
 73  \w     37.00 103.00   0.50    3.14    --   79.75-114.00 171.05  132
 74  \w     52.00 106.00   0.50    3.14    --   79.75-120.00 -43.72  108
 75  \w     38.00 105.00   0.50    3.14    --   79.75-118.00 140.66  134
;
_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      0.0451095000
_diffrn_orient_matrix_UB_12      -0.0991146000
_diffrn_orient_matrix_UB_13      -0.0230441000
_diffrn_orient_matrix_UB_21      -0.0395176000
_diffrn_orient_matrix_UB_22      -0.1275683000
_diffrn_orient_matrix_UB_23      0.0136485000
_diffrn_orient_matrix_UB_31      -0.0517914000
_diffrn_orient_matrix_UB_32      0.0110042000
_diffrn_orient_matrix_UB_33      -0.0493249000
_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  0.0683
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            123316
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.031
_diffrn_reflns_theta_min         2.272
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.777
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.657
_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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.147
_exptl_crystal_description       needle
_exptl_crystal_F_000             1924
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.753
_refine_diff_density_min         -0.504
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     646
_refine_ls_number_reflns         10649
_refine_ls_number_restraints     228
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0651
_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^)+(0.1654P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2052
_refine_ls_wR_factor_ref         0.2152
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8864
_reflns_number_total             10649
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           dippbdimg(dmap)2fp_p21c
_cod_original_formula_sum        'C52 H69 Fe Mg N6 O2.50'
_cod_database_code               1577046
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C54H73FeMgN6O3
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.521
_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. Restrained distances
 O3-C3 = O3-C6
 1.44 with sigma of 0.02
 C3-C4 = C5-C6
 1.53 with sigma of 0.02
 C4-C5
 1.54 with sigma of 0.02
 O3-C4 = O3-C5 = C3-C5 = C4-C6
 2.38 with sigma of 0.04
 C3-C4 \\sim C4-C5 \\sim C5-C6
 with sigma of 0.02
 O3-C3 \\sim O3-C6
 with sigma of 0.02
 O3-C4 \\sim O3-C5
 with sigma of 0.04
 C4-C6 \\sim C3-C5
 with sigma of 0.04
 C01J-C01M \\sim C8-C7
 with sigma of 0.02
 C01J-C01O \\sim C8-C01P
 with sigma of 0.02
 C01K-C01M \\sim C10-C7
 with sigma of 0.02
 C01K-C01N \\sim C10-C9
 with sigma of 0.02
 C01N-C01O \\sim C9-C01P
 with sigma of 0.02
 Fe1-C01J \\sim Fe1-C8
 with sigma of 0.04
 Fe1-C01K \\sim Fe1-C10
 with sigma of 0.04
 Fe1-C01M \\sim Fe1-C7
 with sigma of 0.04
 Fe1-C01N \\sim Fe1-C9
 with sigma of 0.04
 Fe1-C01O \\sim Fe1-C01P
 with sigma of 0.04
 C01J-C01K \\sim C8-C10
 with sigma of 0.04
 C01J-C01N \\sim C8-C9
 with sigma of 0.04
 C01K-C01O \\sim C10-C01P
 with sigma of 0.04
 C01M-C01N \\sim C7-C9
 with sigma of 0.04
 C01M-C01O \\sim C7-C01P
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C01M \\sim C01J \\sim C01O \\sim C01N \\sim C01K: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O1 \\sim C1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
O3 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O3 \\sim C6 \\sim C5 \\sim C4 \\sim C3: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C01N \\sim C01P \\sim C01O \\sim C8 \\sim C7 \\sim C01M \\sim C10 \\sim C01K
\\sim C9: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C5 \\sim C4 \\sim C3 \\sim O3 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O3, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C01P)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C7)=Sof(H7A)=Sof(C8)=
 Sof(H8A)=1-FVAR(1)
 Sof(C01J)=Sof(H3)=Sof(C01K)=Sof(H4)=Sof(C01M)=Sof(H5)=Sof(C01N)=Sof(H6)=
 Sof(C01O)=Sof(H7)=FVAR(1)
 Fixed Sof: O3(0.5) C3(0.5) H3A(0.5) H3B(0.5) C4(0.5) H4B(0.5) H4A(0.5)
 C5(0.5) H5A(0.5) H5B(0.5) C6(0.5) H6A(0.5) H6B(0.5)
6.a Ternary CH refined with riding coordinates:
 C00K(H00K), C00V(H00V), C00Y(H00Y), C019(H019)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4B,H4A), C5(H5A,H5B), C6(H6A,H6B)
6.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00I(H00I), C00L(H00L), C00O(H00O), C00P(H00P),
 C00S(H00S), C00T(H00T), C00W(H00W), C00Z(H00Z), C010(H010), C011(H011),
 C01B(H01S), C01D(H01W), C01J(H3), C01K(H4), C01M(H5), C01N(H6), C01O(H7),
 C01P(H8), C9(H9), C10(H10), C7(H7A), C8(H8A)
6.d Idealised Me refined as rotating group:
 C00U(H00A,H00D,H00E), C00X(H00F,H00G,H00H), C012(H01A,H01B,H01C), C014(H01D,
 H01E,H01F), C015(H01G,H01H,H01I), C016(H01J,H01K,H01L), C017(H01M,H01N,H01O),
 C018(H01P,H01Q,H01R), C01C(H01T,H01U,H01V), C01E(H01X,H01Y,H), C01G(H01Z,HA,
 HB), C01H(H01,HC,HD), C01I(H1,HE,HF), C01L(H2,HG,HH)
;
_shelx_res_checksum              42985
_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 1.667
_oxdiff_exptl_absorpt_empirical_full_min 0.707