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_1577040
_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         'C34 H42 Fe Mg N2 O3'
_chemical_formula_sum            'C34 H42 Fe Mg N2 O3'
_chemical_formula_weight         606.85
_chemical_name_systematic        MesBDIMg(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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2026-02-09 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                106.3340(10)
_cell_angle_beta                 92.7840(10)
_cell_angle_gamma                99.6710(10)
_cell_formula_units_Z            2
_cell_length_a                   8.77690(10)
_cell_length_b                   10.5371(2)
_cell_length_c                   17.7916(2)
_cell_measurement_reflns_used    15748
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.5270
_cell_measurement_theta_min      2.5980
_cell_volume                     1548.57(4)
_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 0.996
_diffrn_measured_fraction_theta_max 0.979
_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     60.00  86.00   0.50    0.19    --   79.75-148.00-155.21   52
  2  \w     48.00  74.00   0.50    0.19    --   79.75-128.00-159.04   52
  3  \w     76.00 109.00   0.50    0.19    --   79.75-128.00-159.04   66
  4  \w     23.00  58.00   0.50    0.19    --   62.61-111.00-123.00   70
  5  \w     41.00  66.00   0.50    0.19    --   75.87-111.00-123.00   50
  6  \w     40.00  65.00   0.50    0.19    --   75.36-111.00-123.00   50
  7  \w     49.00  94.00   0.50    0.19    --   79.75-107.00 -41.35   90
  8  \w     55.00 106.00   0.50    0.19    --   79.75-123.00  38.93  102
  9  \w     26.00  71.00   0.50    0.19    --   62.61 -95.00 150.00   90
 10  \w     40.00  87.00   0.50    0.19    --   79.75-116.00 159.64   94
 11  \w     60.00  98.00   0.50    0.19    --   79.75-111.00 134.83   76
 12  \w     28.00  54.00   0.50    0.19    --   62.61 -95.00 120.00   52
 13  \w     25.00  52.00   0.50    0.19    --   62.61 -95.00  90.00   54
 14  \w     38.00  63.00   0.50    0.19    --   75.87 -95.00 120.00   50
 15  \w     26.00  62.00   0.50    0.19    --   62.61 -95.00 -30.00   72
 16  \w     32.00  70.00   0.50    0.19    --   62.61 -95.00 -90.00   76
 17  \w     38.00  63.00   0.50    0.19    --   75.36 -95.00-180.00   50
 18  \w     43.00  72.00   0.50    0.19    --   79.75 -70.00-137.54   58
 19  \w     46.00  92.00   0.50    0.19    --   79.75  -2.00 -12.31   92
 20  \w     61.00 100.00   0.50    0.19    --   62.61   0.00  60.00   78
 21  \w     68.00  93.00   0.50    0.19    --   79.75  23.00 126.41   50
 22  \w     98.00 126.00   0.50    0.19    --   79.75  23.00 126.41   56
 23  \w    101.00 126.00   0.50    0.19    --   79.75  22.00  30.97   50
 24  \w     64.00  89.00   0.50    0.19    --   62.61  15.00  30.00   50
 25  \w     82.00 108.00   0.50    0.19    --   75.87  15.00  90.00   52
 26  \w     64.00  96.00   0.50    0.19    --   79.75  21.00  -0.23   64
 27  \w     33.00  58.00   0.50    0.19    --   62.61  15.00 -30.00   50
 28  \w     80.00 120.00   0.50    0.19    --   79.75  15.00  24.61   80
 29  \w     76.00 106.00   0.50    0.19    --   62.61  15.00 -30.00   60
 30  \w     49.00 106.00   0.50    0.19    --   79.75  14.00 -36.16  114
 31  \w     65.00 105.00   0.50    0.19    --   78.00  23.00-121.26   80
 32  \w     60.00 119.00   0.50    0.19    --   79.75   6.00-157.61  118
 33  \w     82.00 125.00   0.50    0.19    --   79.75  14.00-120.15   86
 34  \w     25.00  52.00   0.50    0.19    --   62.61   0.00  60.00   54
 35  \w    -76.00 -51.00   0.50    0.19    --  -78.25 155.00 102.61   50
 36  \w    -68.00 -43.00   0.50    0.19    --  -78.25 136.00 168.55   50
 37  \w   -102.00 -77.00   0.50    0.19    --  -78.25 143.00 145.65   50
 38  \w   -113.00 -88.00   0.50    0.19    --  -78.25 136.00 168.55   50
 39  \w   -125.00 -91.00   0.50    0.19    --  -78.25 155.00 102.61   68
 40  \w    -97.00 -70.00   0.50    0.19    --  -73.68 125.00  30.00   54
 41  \w   -113.00 -67.00   0.50    0.19    --  -78.25 136.00 -10.25   92
 42  \w    -70.00 -37.00   0.50    0.19    --  -78.25 140.00 -39.94   66
 43  \w   -110.00 -85.00   0.50    0.19    --  -78.25 132.00 -86.73   50
 44  \w   -109.00 -84.00   0.50    0.19    --  -78.25 130.00-120.65   50
 45  \w   -100.00 -69.00   0.50    0.19    --  -73.68 125.00-180.00   62
 46  \w    -62.00 -37.00   0.50    0.19    --  -73.68 125.00-180.00   50
 47  \w    -96.00 -54.00   0.50    0.19    --  -78.25 122.00 -77.49   84
 48  \w    -92.00 -59.00   0.50    0.19    --  -78.25 115.00-134.76   66
 49  \w    -95.00 -69.00   0.50    0.19    --  -78.25 119.00  10.96   52
 50  \w   -100.00 -52.00   0.50    0.19    --  -78.25 117.00  41.30   96
 51  \w    -57.00 -32.00   0.50    0.19    --  -73.68 125.00  30.00   50
 52  \w    -95.00 -45.00   0.50    0.19    --  -78.25 116.00   2.15  100
 53  \w    -90.00 -55.00   0.50    0.19    --  -73.68 111.00 -29.00   70
 54  \w    -81.00 -40.00   0.50    0.19    --  -78.25 115.00-115.60   82
 55  \w    -55.00 -24.00   0.50    0.19    --  -63.52 111.00 -29.00   62
 56  \w    -91.00 -65.00   0.50    0.19    --  -76.46 111.00 -29.00   52
 57  \w   -108.00 -82.00   0.50    0.19    --  -63.52 -15.00   0.00   52
 58  \w   -110.00 -81.00   0.50    0.19    --  -78.25 -80.00 -25.28   58
 59  \w   -110.00 -85.00   0.50    0.19    --  -78.25 -30.00-102.16   50
 60  \w   -119.00 -94.00   0.50    0.19    --  -78.25 -47.00-131.53   50
 61  \w   -120.00 -94.00   0.50    0.19    --  -78.25 -54.00-173.95   52
 62  \w   -120.00 -95.00   0.50    0.19    --  -78.25 -31.00-178.93   50
 63  \w    -65.00 -34.00   0.50    0.19    --  -63.52 -15.00   0.00   62
 64  \w   -112.00 -79.00   0.50    0.19    --  -78.25 -85.00  20.96   66
 65  \w   -114.00 -80.00   0.50    0.19    --  -78.25 -91.00  53.53   68
 66  \w   -116.00 -74.00   0.50    0.19    --  -76.46-125.00   0.00   84
 67  \w    -74.00 -48.00   0.50    0.19    --  -78.25-174.00 -32.14   52
 68  \w    -99.00 -73.00   0.50    0.19    --  -76.46-125.00 -60.00   52
 69  \w   -112.00 -87.00   0.50    0.19    --  -78.25 -90.00 -67.73   50
 70  \w   -112.00 -87.00   0.50    0.19    --  -78.25 -91.00-154.49   50
;
_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      0.1123023000
_diffrn_orient_matrix_UB_12      0.1367373000
_diffrn_orient_matrix_UB_13      0.0203513000
_diffrn_orient_matrix_UB_21      0.0364699000
_diffrn_orient_matrix_UB_22      -0.0301089000
_diffrn_orient_matrix_UB_23      -0.0863929000
_diffrn_orient_matrix_UB_31      -0.1344994000
_diffrn_orient_matrix_UB_32      0.0668767000
_diffrn_orient_matrix_UB_33      -0.0186578000
_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  0.0224
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            31265
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.178
_diffrn_reflns_theta_min         2.601
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.385
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.851
_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    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             644
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.186
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         6261
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0492P)^2^+0.4497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0845
_refine_ls_wR_factor_ref         0.0858
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5856
_reflns_number_total             6261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg106_p1-
_cod_original_cell_volume        1548.56(4)
_cod_database_code               1577040
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H42 Fe Mg N2 O3'
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.599
_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:
 C00P(H00a,H00b), C00V(H00q,H00r), C00Z(H00w,H00z), C012(H01d,H01e)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C00F(H00F), C00G(H00G), C00K(H00K), C00L(H00L), C00O(H00O),
 C00U(H00U), C00X(H00X), C00Y(H00Y), C010(H010)
2.c Idealised Me refined as rotating group:
 C00Q(H00c,H00d,H00e), C00S(H00h,H00i,H00j), C00T(H00m,H00n,H00p), C00W(H00s,
 H00t,H00v), C011(H01a,H01b,H01c), C013(H01f,H01g,H01h), C014(H01i,H01j,H01k),
 C015(H01l,H01m,H01n)
;
_shelx_res_checksum              69121
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.864