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_1577039
_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         'C21 H42 Fe O2 P4 Si4'
_chemical_formula_sum            'C21 H42 Fe O2 P4 Si4'
_chemical_formula_weight         618.63
_chemical_name_systematic        '[Fp*{P4Si(SiMe3)3}]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-13
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2026-02-09 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.9165(2)
_cell_length_b                   16.5219(3)
_cell_length_c                   27.4951(5)
_cell_measurement_reflns_used    19834
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.9300
_cell_measurement_theta_min      3.1380
_cell_volume                     6776.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 44.100a 64-bit (release 20-03-2025))'
_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     65.00 126.00   0.50    1.61    --   79.75  22.00 110.20  122
  2  \w     58.00 126.00   0.50    1.61    --   79.75  20.00   9.29  136
  3  \w     32.00  60.00   0.50    1.61    --   63.06  15.00   0.00   56
  4  \w     66.00 108.00   0.50    1.61    --   63.06  15.00   0.00   84
  5  \w     26.00 100.00   0.50    1.61    --   63.06   0.00 -60.00  148
  6  \w     44.00 117.00   0.50    1.61    --   79.75   0.00  84.01  146
  7  \w     85.00 112.00   0.50    1.61    --   79.75  -3.00 157.78   54
  8  \w     47.00  84.00   0.50    1.61    --   75.94-110.00 -41.00   74
  9  \w     50.00  75.00   0.50    1.61    --   63.06-110.00 -41.00   50
 10  \w     41.00  84.00   0.50    1.61    --   79.75  -3.00 157.78   86
 11  \w    -82.00 -35.00   0.50    1.61    --  -73.72 125.00 150.00   94
 12  \w    -79.00 -42.00   0.50    1.61    --  -78.25  88.00  69.62   74
 13  \w    -95.00 -68.00   0.50    1.61    --  -76.78 110.00  53.00   54
 14  \w    -71.00 -44.00   0.50    1.61    --  -73.72 110.00  53.00   54
 15  \w    -53.00 -23.00   0.50    1.61    --  -63.96 110.00  53.00   60
 16  \w   -100.00 -51.00   0.50    1.61    --  -78.25 118.00 -69.89   98
;
_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      -0.0235722000
_diffrn_orient_matrix_UB_12      0.0062540000
_diffrn_orient_matrix_UB_13      0.0544438000
_diffrn_orient_matrix_UB_21      0.0660240000
_diffrn_orient_matrix_UB_22      0.0712140000
_diffrn_orient_matrix_UB_23      0.0054562000
_diffrn_orient_matrix_UB_31      -0.0759184000
_diffrn_orient_matrix_UB_32      0.0598829000
_diffrn_orient_matrix_UB_33      -0.0121157000
_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  0.0624
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            38011
_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         74.989
_diffrn_reflns_theta_min         3.215
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.839
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.698
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             2608
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane'
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.395
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         6849
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0563
_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^)+(0.0645P)^2^+13.4773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1472
_refine_ls_wR_factor_ref         0.1505
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5830
_reflns_number_total             6849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg203_auto
_cod_database_code               1577039
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H42FeO2P4Si4
_shelx_estimated_absorpt_t_max   0.548
_shelx_estimated_absorpt_t_min   0.218
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C00I(H00A,H00B,H00C), C00K(H00D,H00E,H00F), C00L(H00G,H00H,H00I), C00M(H00J,
 H00K,H00L), C00N(H00M,H00N,H00O), C00O(H00P,H00Q,H00R), C00P(H00S,H00T,H00U),
 C00Q(H00V,H00W,H00X), C00R(H00Y,H,HA), C00S(H00Z,HB,HC), C00T(H00,HD,HE),
 C00U(H1,HF,HG), C00V(H2,HH,HI), C00W(H3,HJ,HK)
;
_shelx_res_checksum              28984
_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 1.656
_oxdiff_exptl_absorpt_empirical_full_min 0.697