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_1577042
_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         'C45 H66 Fe Mg N2 O4'
_chemical_formula_sum            'C45 H66 Fe Mg N2 O4'
_chemical_formula_weight         779.15
_chemical_name_systematic        DippBDIMg(DME)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   mixed
_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                97.2210(10)
_cell_angle_beta                 91.1710(10)
_cell_angle_gamma                107.4110(10)
_cell_formula_units_Z            2
_cell_length_a                   9.07320(10)
_cell_length_b                   12.9510(2)
_cell_length_c                   19.3861(2)
_cell_measurement_reflns_used    24229
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.6700
_cell_measurement_theta_min      2.3470
_cell_volume                     2152.33(5)
_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   -109.00 -76.00   0.50    0.31    --  -63.52 -15.00  60.00   66
  2  \w    -71.00 -33.00   0.50    0.31    --  -63.52 -15.00  60.00   76
  3  \w   -108.00 -44.00   0.50    0.31    --  -63.52 -15.00   0.00  128
  4  \w   -121.00 -95.00   0.50    0.31    --  -78.25 -52.00-142.42   52
  5  \w   -109.00 -32.00   0.50    0.31    --  -63.52 -15.00-150.00  154
  6  \w   -104.00 -36.00   0.50    0.31    --  -73.68   0.00 -90.00  136
  7  \w    -74.00 -33.00   0.50    0.31    --  -63.52 138.00 -51.00   82
  8  \w   -109.00 -45.00   0.50    0.31    --  -73.68 138.00 -51.00  128
  9  \w    -98.00 -73.00   0.50    0.31    --  -76.46 138.00 -51.00   50
 10  \w    -57.00 -32.00   0.50    0.31    --  -73.68 125.00   0.00   50
 11  \w    -82.00 -56.00   0.50    0.31    --  -76.46 132.00 132.00   52
 12  \w   -104.00 -55.00   0.50    0.31    --  -73.68 132.00 132.00   98
 13  \w    -95.00 -56.00   0.50    0.31    --  -63.52 132.00 132.00   78
 14  \w   -100.00 -61.00   0.50    0.31    --  -73.68 125.00   0.00   78
 15  \w    -64.00 -34.00   0.50    0.31    --  -73.68 125.00-180.00   60
 16  \w   -100.00 -74.00   0.50    0.31    --  -73.68 125.00-180.00   52
 17  \w    -83.00 -58.00   0.50    0.31    --  -78.25  98.00-174.83   50
 18  \w    -61.00 -36.00   0.50    0.31    --  -78.25  57.00-101.73   50
 19  \w     32.00  63.00   0.50    0.31    --   62.61-138.00-113.00   62
 20  \w     49.00  74.00   0.50    0.31    --   75.87-138.00-113.00   50
 21  \w     40.00  72.00   0.50    0.31    --   79.75-130.00 -44.84   64
 22  \w     82.00 107.00   0.50    0.31    --   79.75-130.00 -44.84   50
 23  \w     38.00 106.00   0.50    0.31    --   79.75-126.00 -92.25  136
 24  \w     37.00  79.00   0.50    0.31    --   79.75-126.00-163.40   84
 25  \w     38.00 103.00   0.50    0.31    --   79.75-128.00  21.69  130
 26  \w     79.00 105.00   0.50    0.31    --   79.75-122.00  37.50   52
 27  \w     70.00  99.00   0.50    0.31    --   75.87-132.00  63.00   58
 28  \w     45.00 108.00   0.50    0.31    --   79.75-126.00 100.90  126
 29  \w     34.00  59.00   0.50    0.31    --   62.61-132.00  63.00   50
 30  \w     38.00  64.00   0.50    0.31    --   79.75-122.00  37.50   52
 31  \w     42.00 104.00   0.50    0.31    --   79.75-120.00 -19.00  124
 32  \w     40.00 104.00   0.50    0.31    --   79.75-121.00-148.24  128
 33  \w     50.00  95.00   0.50    0.31    --   79.75-120.00-107.54   90
 34  \w     65.00  91.00   0.50    0.31    --   79.75-118.00 -67.68   52
 35  \w     49.00  83.00   0.50    0.31    --   79.75-121.00 -44.39   68
 36  \w     41.00  73.00   0.50    0.31    --   79.75-118.00   0.42   64
 37  \w     41.00  99.00   0.50    0.31    --   79.75-117.00  41.06  116
 38  \w     40.00  95.00   0.50    0.31    --   79.75-115.00  69.91  110
 39  \w     50.00 102.00   0.50    0.31    --   79.75-117.00 117.77  104
 40  \w     41.00  93.00   0.50    0.31    --   79.75-116.00 179.23  104
 41  \w     44.00  96.00   0.50    0.31    --   79.75-119.00 162.26  104
 42  \w     54.00  85.00   0.50    0.31    --   79.75-119.00 139.87   62
 43  \w     27.00  71.00   0.50    0.31    --   62.61 -95.00 120.00   88
 44  \w     28.00  68.00   0.50    0.31    --   62.61 -95.00 -30.00   80
 45  \w     27.00  68.00   0.50    0.31    --   62.61 -95.00 -90.00   82
 46  \w     40.00 116.00   0.50    0.31    --   79.75  -3.00 -31.62  152
 47  \w     71.00  96.00   0.50    0.31    --   75.87 138.00 -51.00   50
 48  \w     42.00  84.00   0.50    0.31    --   79.75  -4.00 -73.81   84
 49  \w     50.00  77.00   0.50    0.31    --   79.75  -4.00  43.13   54
 50  \w     51.00 122.00   0.50    0.31    --   79.75   8.00  13.93  142
 51  \w     64.00 119.00   0.50    0.31    --   79.75  21.00 142.63  110
 52  \w    101.00 126.00   0.50    0.31    --   79.75  18.00 -83.55   50
 53  \w     68.00 104.00   0.50    0.31    --   79.75  13.00-117.50   72
 54  \w     54.00  84.00   0.50    0.31    --   79.75  18.00 -83.55   60
 55  \w   -114.00 -89.00   0.50    0.31    --  -73.68-138.00-113.00   50
 56  \w   -116.00 -91.00   0.50    0.31    --  -76.46-138.00-113.00   50
 57  \w   -118.00 -93.00   0.50    0.31    --  -76.46-132.00  63.00   50
 58  \w   -109.00 -79.00   0.50    0.31    --  -73.68-132.00  63.00   60
;
_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      -0.0485794000
_diffrn_orient_matrix_UB_12      -0.1258029000
_diffrn_orient_matrix_UB_13      -0.0111021000
_diffrn_orient_matrix_UB_21      0.0005444000
_diffrn_orient_matrix_UB_22      -0.0001016000
_diffrn_orient_matrix_UB_23      0.0794635000
_diffrn_orient_matrix_UB_31      -0.1715345000
_diffrn_orient_matrix_UB_32      -0.0041790000
_diffrn_orient_matrix_UB_33      -0.0017186000
_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  0.0240
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            44674
_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         75.271
_diffrn_reflns_theta_min         2.302
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.277
_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 reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_description       plank
_exptl_crystal_F_000             840
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DME'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.349
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     520
_refine_ls_number_reflns         8747
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0452P)^2^+0.6159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0877
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8130
_reflns_number_total             8747
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg110_dme_p1-
_cod_database_code               1577042
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C45H66FeMgN2O4
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.461
_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
 C012-C01G \\sim C012-C6
 with sigma of 0.02
 C012-C01H \\sim C012-C01I
 with sigma of 0.02
3. Others
 Sof(H01C)=Sof(C01I)=Sof(H6)=Sof(HM)=Sof(HN)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(H6C)=1-FVAR(1)
 Sof(H012)=Sof(C01G)=Sof(H3)=Sof(HI)=Sof(HJ)=Sof(C01H)=Sof(H5)=Sof(HK)=Sof(HL)=
 FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C00L(H00L), C00X(H00X), C010(H010), C012(H01C), C012(H012)
4.b Secondary CH2 refined with riding coordinates:
 C011(H01A,H01B), C016(H01M,H01N)
4.c Aromatic/amide H refined with riding coordinates:
 C00M(H00M), C00P(H00P), C00R(H00R), C00W(H00W), C00Z(H00Z), C019(H019)
4.d Idealised Me refined as rotating group:
 C00N(H00A,H00B,H00C), C00S(H00D,H00E,H00F), C00T(H00G,H00H,H00I), C00Y(H00J,
 H00K,H00N), C013(H01D,H01E,H01F), C014(H01G,H01H,H01I), C015(H01J,H01K,H01L),
 C017(H01O,H01P,H01Q), C018(H01R,H01S,H01T), C01A(H01U,H01V,H01W), C01B(H01X,
 H01Y,H), C01C(H01Z,HA,HB), C01D(H01,HC,HD), C01E(H1,HE,HF), C01F(H2,HG,HH),
 C01G(H3,HI,HJ), C01H(H5,HK,HL), C01I(H6,HM,HN), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              76543
_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 1.671
_oxdiff_exptl_absorpt_empirical_full_min 0.729