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_1577038
_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         'C40 H54 Fe Mg N2 O3 P4, C4 H8 O'
_chemical_formula_sum            'C44 H62 Fe Mg N2 O4 P4'
_chemical_formula_weight         886.99
_chemical_name_systematic        DippBDIMg(THF)FpP4
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-27
_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                 91.8370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.2780(2)
_cell_length_b                   13.07050(10)
_cell_length_c                   38.5592(4)
_cell_measurement_reflns_used    28165
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      75.1690
_cell_measurement_theta_min      2.3680
_cell_volume                     9207.16(16)
_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 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 0.981
_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     62.00 114.00   0.50    0.73    --   79.75  21.00-154.01  104
  2  \w     64.00 126.00   0.50    0.73    --   79.75  22.00-104.31  124
  3  \w     61.00 121.00   0.50    0.73    --   79.75  21.00 -29.58  120
  4  \w     80.00 117.00   0.50    0.73    --   79.75  20.00   9.89   74
  5  \w     72.00 120.00   0.50    0.73    --   79.75  21.00  57.32   96
  6  \w     69.00 101.00   0.50    0.73    --   79.75  19.00 125.60   64
  7  \w     65.00 104.00   0.50    0.73    --   79.75  22.00 160.33   78
  8  \w     88.00 118.00   0.50    0.73    --   79.75   7.00 152.20   60
  9  \w     46.00  81.00   0.50    0.73    --   79.75   7.00 152.20   70
 10  \w     35.00  98.00   0.50    0.73    --   62.92   0.00  60.00  126
 11  \w     41.00  69.00   0.50    0.73    --   79.75  -2.00-116.44   56
 12  \w     72.00 100.00   0.50    0.73    --   79.75  -2.00-116.44   56
 13  \w     40.00  82.00   0.50    0.73    --   79.75  -4.00-178.25   84
 14  \w     25.00  59.00   0.50    0.73    --   62.92 -95.00-150.00   68
 15  \w     32.00  57.00   0.50    0.73    --   62.92-125.00 -90.00   50
 16  \w     64.00  90.00   0.50    0.73    --   62.92-125.00 -90.00   52
 17  \w     25.00  70.00   0.50    0.73    --   62.92 -95.00 -60.00   90
 18  \w   -112.00 -87.00   0.50    0.73    --  -78.25 -82.00 -39.31   50
 19  \w   -111.00 -85.00   0.50    0.73    --  -78.25 -84.00  61.62   52
 20  \w    -94.00 -62.00   0.50    0.73    --  -63.82   0.00 -30.00   64
 21  \w    -54.00 -28.00   0.50    0.73    --  -63.82   0.00 -30.00   52
 22  \w    -61.00 -36.00   0.50    0.73    --  -78.25  56.00 155.67   50
 23  \w    -79.00 -45.00   0.50    0.73    --  -78.25  88.00  82.89   68
 24  \w    -83.00 -36.00   0.50    0.73    --  -63.82 125.00  90.00   94
 25  \w    -97.00 -59.00   0.50    0.73    --  -78.25 122.00  74.33   76
 26  \w    -91.00 -64.00   0.50    0.73    --  -78.25 120.00  91.29   54
 27  \w    -96.00 -49.00   0.50    0.73    --  -78.25 113.00 125.48   94
 28  \w    -77.00 -43.00   0.50    0.73    --  -78.25  97.00  49.48   68
 29  \w    -94.00 -69.00   0.50    0.73    --  -73.68 125.00-120.00   50
 30  \w    -65.00 -39.00   0.50    0.73    --  -73.68 125.00-120.00   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      0.0461160000
_diffrn_orient_matrix_UB_12      0.0230863000
_diffrn_orient_matrix_UB_13      0.0332013000
_diffrn_orient_matrix_UB_21      -0.0612396000
_diffrn_orient_matrix_UB_22      -0.0438424000
_diffrn_orient_matrix_UB_23      0.0221475000
_diffrn_orient_matrix_UB_31      0.0351633000
_diffrn_orient_matrix_UB_32      -0.1069966000
_diffrn_orient_matrix_UB_33      -0.0018371000
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            42973
_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         75.286
_diffrn_reflns_theta_min         3.571
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.404
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.430
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             3760
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: THF/n-hexane'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.629
_refine_diff_density_min         -0.289
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     571
_refine_ls_number_reflns         9348
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0712P)^2^+10.2929P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1214
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8643
_reflns_number_total             9348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           dippmgfpp4_i2_a
_cod_database_code               1577038
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H54 Mg Fe N2 O P4'
_shelx_estimated_absorpt_t_max   0.643
_shelx_estimated_absorpt_t_min   0.406
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4-C8 \\sim O1A-C3A
 with sigma of 0.02
 O4-C10 \\sim O1A-C5A
 with sigma of 0.02
 C6-C8 \\sim C1A-C3A
 with sigma of 0.02
 C6-C9 \\sim C1A-C4A
 with sigma of 0.02
 C9-C10 \\sim C4A-C5A
 with sigma of 0.02
 O4-C6 \\sim O1A-C1A
 with sigma of 0.04
 O4-C9 \\sim O1A-C4A
 with sigma of 0.04
 C6-C10 \\sim C1A-C5A
 with sigma of 0.04
 C8-C9 \\sim C3A-C4A
 with sigma of 0.04
 C8-C10 \\sim C3A-C5A
 with sigma of 0.04
 C00H-C00N \\sim C00H-C7
 with sigma of 0.02
 C00N-C00S \\sim C7-C00S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C10 \\sim O4 \\sim C8 \\sim C6 \\sim C9 \\sim O1A \\sim C5A \\sim C4A \\sim C1A
\\sim C3A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
4. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(O1A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C1A)=
 Sof(H1AA)=Sof(H1AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-FVAR(1)
 Sof(O4)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=
 Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=FVAR(1)
 Sof(H00C)=Sof(H00D)=Sof(H00K)=Sof(H00L)=Sof(C7)=Sof(H7A)=Sof(H7B)=1-FVAR(2)
 Sof(H00A)=Sof(H00B)=Sof(C00N)=Sof(H00G)=Sof(H00H)=Sof(H00I)=Sof(H00J)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C00M(H00M), C00X(H00X), C00Y(H00Y), C011(H011)
5.b Secondary CH2 refined with riding coordinates:
 C00H(H00A,H00B), C00H(H00C,H00D), C00L(H00E,H00F), C00N(H00G,H00H), C00S(H00I,
 H00J), C00S(H00K,H00L), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B),
 C3A(H3AA,H3AB), C5A(H5AA,H5AB), C1A(H1AA,H1AB), C4A(H4AA,H4AB), C7(H7A,H7B)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C00P(H00P), C00R(H00R), C00V(H00V), C00W(H00W), C010(H010),
 C012(H012), C015(H015), C019(H019), C01C(H01V), C01D(H01W), C01F(H01Z)
5.d Idealised Me refined as rotating group:
 C00T(H00N,H00O,H00Q), C00U(H00S,H00T,H00U), C013(H01A,H01B,H01C), C014(H01D,
 H01E,H01F), C016(H01G,H01H,H01I), C017(H01J,H01K,H01L), C018(H01M,H01N,H01O),
 C01A(H01P,H01Q,H01R), C01B(H01S,H01T,H01U), C01E(H01X,H01Y,H)
;
_shelx_res_checksum              29766
_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 1.295
_oxdiff_exptl_absorpt_empirical_full_min 0.800