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_1577048
_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         'C84 H104 Fe2 O4 P8 Sn2'
_chemical_formula_sum            'C84 H104 Fe2 O4 P8 Sn2'
_chemical_formula_weight         1774.51
_chemical_name_systematic        '[{Cp*Fe(CO)2}2(Ar2Sn2P8)]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2025-05-22
_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                 113.6400(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.02810(10)
_cell_length_b                   42.02450(10)
_cell_length_c                   15.35080(10)
_cell_measurement_reflns_used    117460
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      75.1200
_cell_measurement_theta_min      3.1290
_cell_volume                     8290.24(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_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 1.000
_diffrn_measured_fraction_theta_max 0.987
_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  52.00   0.50    0.34    --   62.87-125.00 150.00   52
  2  \w     54.00  80.00   0.50    0.34    --   62.87-125.00 150.00   52
  3  \w     25.00  62.00   0.50    0.34    --   62.87 -95.00 -90.00   74
  4  \w     29.00  69.00   0.50    0.34    --   62.87 -95.00-180.00   80
  5  \w     27.00  67.00   0.50    0.34    --   62.87-125.00-120.00   80
  6  \w     25.00  50.00   0.50    0.34    --   62.87 -95.00 -60.00   50
  7  \w     43.00  69.00   0.50    0.34    --   75.95 -95.00 -30.00   52
  8  \w     43.00  75.00   0.50    0.34    --   75.39 -95.00  30.00   64
  9  \w     26.00  52.00   0.50    0.34    --   62.87 -95.00 150.00   52
 10  \w     40.00  68.00   0.50    0.34    --   79.75  -4.00 177.67   56
 11  \w     52.00  81.00   0.50    0.34    --   79.75  -4.00 134.81   58
 12  \w     41.00  82.00   0.50    0.34    --   79.75  -4.00 106.53   82
 13  \w     40.00  78.00   0.50    0.34    --   79.75  -4.00  17.00   76
 14  \w     46.00  72.00   0.50    0.34    --   79.75  -4.00 -30.15   52
 15  \w     42.00  96.00   0.50    0.34    --   79.75  -1.00  50.24  108
 16  \w     49.00  79.00   0.50    0.34    --   79.75  -4.00 -62.85   60
 17  \w     41.00  85.00   0.50    0.34    --   79.75  -2.00 -96.98   88
 18  \w     56.00  81.00   0.50    0.34    --   79.75  -4.00-170.41   50
 19  \w     99.00 126.00   0.50    0.34    --   79.75  23.00-173.99   54
 20  \w     70.00  95.00   0.50    0.34    --   79.75  22.00-158.94   50
 21  \w     65.00  91.00   0.50    0.34    --   79.75  21.00 -77.78   52
 22  \w     70.00 104.00   0.50    0.34    --   79.75  15.00-110.31   68
 23  \w     62.00 126.00   0.50    0.34    --   79.75  21.00  -1.96  128
 24  \w     63.00 108.00   0.50    0.34    --   79.75  21.00  59.49   90
 25  \w     53.00  79.00   0.50    0.34    --   79.75  10.00  85.36   52
 26  \w     65.00 107.00   0.50    0.34    --   79.75  22.00 168.64   84
 27  \w     64.00 112.00   0.50    0.34    --   79.75  21.00  91.49   96
 28  \w     90.00 116.00   0.50    0.34    --   79.75  10.00  85.36   52
 29  \w     44.00  71.00   0.50    0.34    --   79.75   4.00 -48.03   54
 30  \w     87.00 117.00   0.50    0.34    --   79.75   4.00 -48.03   60
 31  \w     75.00 100.00   0.50    0.34    --   62.87   0.00 -90.00   50
 32  \w     81.00 119.00   0.50    0.34    --   79.75   6.00-177.55   76
 33  \w     52.00  78.00   0.50    0.34    --   79.75   6.00-177.55   52
 34  \w     27.00  55.00   0.50    0.34    --   62.87   0.00 -90.00   56
 35  \w     32.00  80.00   0.50    0.34    --   62.87   0.00  60.00   96
 36  \w    -82.00 -56.00   0.50    0.34    --  -78.25  97.00 144.54   52
 37  \w   -110.00 -80.00   0.50    0.34    --  -78.25 139.00 161.95   60
 38  \w    -63.00 -38.00   0.50    0.34    --  -78.25 139.00 161.95   50
 39  \w    -71.00 -44.00   0.50    0.34    --  -78.25 139.00 103.10   54
 40  \w   -102.00 -73.00   0.50    0.34    --  -78.25 129.00  75.02   58
 41  \w    -68.00 -42.00   0.50    0.34    --  -78.25 129.00  75.02   52
 42  \w    -97.00 -51.00   0.50    0.34    --  -73.66 125.00  60.00   92
 43  \w   -102.00 -43.00   0.50    0.34    --  -78.25 122.00  66.69  118
 44  \w    -73.00 -47.00   0.50    0.34    --  -78.25 125.00 -23.75   52
 45  \w    -72.00 -46.00   0.50    0.34    --  -78.25 125.00 -50.53   52
 46  \w    -97.00 -71.00   0.50    0.34    --  -73.66 125.00-150.00   52
 47  \w    -66.00 -41.00   0.50    0.34    --  -78.25 117.00-114.55   50
 48  \w    -88.00 -28.00   0.50    0.34    --  -63.67 125.00 -90.00  120
 49  \w    -89.00 -41.00   0.50    0.34    --  -78.25 113.00 -29.39   96
 50  \w    -79.00 -40.00   0.50    0.34    --  -78.25 113.00   3.16   78
 51  \w    -87.00 -38.00   0.50    0.34    --  -78.25 112.00 -65.47   98
 52  \w    -75.00 -50.00   0.50    0.34    --  -78.25 115.00  95.74   50
 53  \w    -70.00 -42.00   0.50    0.34    --  -78.25 112.00 112.96   56
 54  \w    -63.00 -38.00   0.50    0.34    --  -78.25 113.00 174.62   50
 55  \w    -66.00 -40.00   0.50    0.34    --  -78.25 111.00 163.35   52
 56  \w    -95.00 -39.00   0.50    0.34    --  -78.25 112.00 140.41  112
 57  \w    -64.00 -39.00   0.50    0.34    --  -78.25 111.00 145.79   50
 58  \w    -69.00 -26.00   0.50    0.34    --  -63.67   0.00 -30.00   86
 59  \w    -63.00 -37.00   0.50    0.34    --  -78.25  61.00-155.09   52
 60  \w    -61.00 -35.00   0.50    0.34    --  -78.25  56.00 130.79   52
 61  \w   -101.00 -73.00   0.50    0.34    --  -63.67   0.00 -30.00   56
 62  \w    -79.00 -54.00   0.50    0.34    --  -63.67 -15.00 -60.00   50
 63  \w   -118.00 -93.00   0.50    0.34    --  -78.25 -66.00 -29.20   50
 64  \w   -110.00 -85.00   0.50    0.34    --  -78.25 -71.00 -16.72   50
 65  \w   -113.00 -88.00   0.50    0.34    --  -78.25 -67.00  -3.13   50
 66  \w   -119.00 -94.00   0.50    0.34    --  -78.25 -42.00  42.80   50
 67  \w   -125.00 -97.00   0.50    0.34    --  -78.25 -35.00  58.71   56
 68  \w   -119.00 -89.00   0.50    0.34    --  -74.00 -40.00 -28.28   60
 69  \w   -108.00 -82.00   0.50    0.34    --  -78.25 -80.00  78.17   52
 70  \w   -114.00 -89.00   0.50    0.34    --  -78.25 -50.00 148.47   50
 71  \w   -124.00 -99.00   0.50    0.34    --  -78.25 -41.00 126.77   50
 72  \w   -107.00 -35.00   0.50    0.34    --  -63.67 -15.00  60.00  144
 73  \w    -67.00 -37.00   0.50    0.34    --  -63.67 -15.00   0.00   60
 74  \w   -108.00 -80.00   0.50    0.34    --  -63.67 -15.00   0.00   56
 75  \w   -105.00 -47.00   0.50    0.34    --  -63.67 -15.00-120.00  116
 76  \w    -97.00 -33.00   0.50    0.34    --  -63.67 -15.00 -90.00  128
 77  \w   -113.00 -88.00   0.50    0.34    --  -78.25 -84.00 124.69   50
 78  \w   -111.00 -82.00   0.50    0.34    --  -78.25 -87.00 155.87   58
 79  \w   -112.00 -87.00   0.50    0.34    --  -78.25 -85.00 177.25   50
 80  \w   -106.00 -80.00   0.50    0.34    --  -78.25-171.00  43.03   52
 81  \w   -109.00 -84.00   0.50    0.34    --  -78.25 -90.00 -48.97   50
 82  \w   -109.00 -83.00   0.50    0.34    --  -78.25 -86.00-142.95   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      -0.0275920000
_diffrn_orient_matrix_UB_12      0.0268583000
_diffrn_orient_matrix_UB_13      -0.0743979000
_diffrn_orient_matrix_UB_21      -0.1127237000
_diffrn_orient_matrix_UB_22      -0.0123445000
_diffrn_orient_matrix_UB_23      -0.0460711000
_diffrn_orient_matrix_UB_31      -0.0300018000
_diffrn_orient_matrix_UB_32      0.0216732000
_diffrn_orient_matrix_UB_33      0.0659531000
_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  0.0241
_diffrn_reflns_av_unetI/netI     0.0114
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            201154
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.283
_diffrn_reflns_theta_min         3.314
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.316
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.665
_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 dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       block
_exptl_crystal_F_000             3648
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/n-hexane'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.634
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     927
_refine_ls_number_reflns         16935
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0222
_refine_ls_R_factor_gt           0.0211
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0303P)^2^+5.5951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0563
_refine_ls_wR_factor_ref         0.0568
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16293
_reflns_number_total             16935
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg142c_p21_c
_cod_database_code               1577048
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C84H104Fe2O4P8Sn2
_shelx_estimated_absorpt_t_max   0.523
_shelx_estimated_absorpt_t_min   0.335
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C018(H018), C019(H019), C01A(H01A), C01J(H01J), C01K(H01K), C01L(H01L),
 C025(H025), C02F(H02y)
2.b Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00J(H00J), C00L(H00L), C012(H012), C015(H015), C016(H016),
 C01B(H01B), C01E(H01E), C01I(H01I), C01Q(H01Q), C01Y(H01Y), C020(H020),
 C022(H022), C027(H027), C029(H029), C02A(H02p), C02D(H02w), C02E(H02x)
2.c Idealised Me refined as rotating group:
 C00W(H00a,H00b,H00c), C00Z(H00d,H00e,H00f), C01H(H01c,H01d,H01f), C01P(H01g,
 H01h,H01m), C01R(H01n,H01o,H01p), C01W(H01r,H01s,H01t), C01X(H01u,H01v,H01w),
 C021(H02a,H02b,H02c), C023(H02d,H02e,H02f), C024(H02g,H02h,H02i), C026(H02j,
 H02k,H02l), C028(H02m,H02n,H02o), C02B(H02q,H02r,H02s), C02C(H02t,H02u,H02v),
 C02G(H02z,H,Ha), C02H(H02,Hb,Hc), C02I(H1,Hd,He), C02J(H2,Hf,Hg), C02L(H3,Hh,
 Hi), C02M(H4,Hj,Hk), C02N(H5,Hl,Hm), C02O(H6,Hn,Ho), C02P(H7,Hp,Hq), C02Q(H8,
 Hr,Hs), C02R(H9,Ht,Hu), C02S(H10,Hv,Hw)
;
_shelx_res_checksum              21946
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.850