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_1577050
_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         '2(C30 H30 Fe O2 P4 Sn)'
_chemical_formula_sum            'C60 H60 Fe2 O4 P8 Sn2'
_chemical_formula_weight         1441.92
_chemical_name_systematic        '[Cp*Fe(CO)2(P4SnPh3)]'
_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             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                90.5130(10)
_cell_angle_beta                 99.0590(10)
_cell_angle_gamma                93.5130(10)
_cell_formula_units_Z            2
_cell_length_a                   9.23480(10)
_cell_length_b                   16.59130(10)
_cell_length_c                   20.4964(2)
_cell_measurement_reflns_used    52783
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.9990
_cell_measurement_theta_min      2.6420
_cell_volume                     3094.85(5)
_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 0.998
_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     38.00  63.00   0.50    0.14    --   79.75-127.00  16.66   50
  2  \w     74.00 108.00   0.50    0.14    --   79.75-127.00  16.66   68
  3  \w     73.00  98.00   0.50    0.14    --   62.87-162.00  33.00   50
  4  \w     76.00 101.00   0.50    0.14    --   75.95-162.00  33.00   50
  5  \w     79.00 108.00   0.50    0.14    --   79.75-126.00  89.68   58
  6  \w     46.00  76.00   0.50    0.14    --   79.75-126.00  89.68   60
  7  \w     40.00  88.00   0.50    0.14    --   79.75-119.00  90.63   96
  8  \w     41.00 102.00   0.50    0.14    --   79.75-118.00 111.50  122
  9  \w     45.00 102.00   0.50    0.14    --   79.75-124.00  56.02  114
 10  \w     46.00 107.00   0.50    0.14    --   79.75-125.00 -31.83  122
 11  \w     40.00  99.00   0.50    0.14    --   79.75-119.00 -55.46  118
 12  \w     42.00  67.00   0.50    0.14    --   75.39-117.00-176.00   50
 13  \w     42.00  67.00   0.50    0.14    --   75.95-117.00-176.00   50
 14  \w     45.00  73.00   0.50    0.14    --   62.87-117.00-176.00   56
 15  \w     42.00  97.00   0.50    0.14    --   79.75-114.00 -82.31  110
 16  \w     34.00  70.00   0.50    0.14    --   62.87 -95.00 -90.00   72
 17  \w     55.00  81.00   0.50    0.14    --   75.39 -95.00-150.00   52
 18  \w     25.00  71.00   0.50    0.14    --   62.87 -95.00-150.00   92
 19  \w     37.00  63.00   0.50    0.14    --   62.87 -95.00  30.00   52
 20  \w     25.00  69.00   0.50    0.14    --   62.87 -95.00  90.00   88
 21  \w     41.00  67.00   0.50    0.14    --   79.75-116.00 127.57   52
 22  \w     73.00 101.00   0.50    0.14    --   79.75-116.00 127.57   56
 23  \w     55.00  99.00   0.50    0.14    --   79.75-113.00 138.01   88
 24  \w     51.00  78.00   0.50    0.14    --   79.75  -4.00 -67.11   54
 25  \w     51.00  78.00   0.50    0.14    --   79.75  -4.00-144.89   54
 26  \w     42.00  71.00   0.50    0.14    --   79.75  -4.00-163.21   58
 27  \w     49.00  81.00   0.50    0.14    --   79.75  -4.00  -1.65   64
 28  \w     41.00  67.00   0.50    0.14    --   79.75  -4.00  83.53   52
 29  \w     43.00  81.00   0.50    0.14    --   79.75  -4.00 120.11   76
 30  \w     59.00  84.00   0.50    0.14    --   75.95 162.00  60.00   50
 31  \w     58.00  83.00   0.50    0.14    --   75.39 162.00  60.00   50
 32  \w     43.00  83.00   0.50    0.14    --   79.75  -4.00-101.66   80
 33  \w     40.00  68.00   0.50    0.14    --   79.75  -4.00 -19.68   56
 34  \w     99.00 127.00   0.50    0.14    --   79.75  22.00 -22.80   56
 35  \w     65.00 106.00   0.50    0.14    --   79.75  21.00-159.92   82
 36  \w     61.00  89.00   0.50    0.14    --   79.75  20.00-116.46   56
 37  \w     62.00 116.00   0.50    0.14    --   79.75  21.00 -87.51  108
 38  \w     33.00 104.00   0.50    0.14    --   62.87  15.00 -30.00  142
 39  \w     51.00  76.00   0.50    0.14    --   79.75  16.00  77.66   50
 40  \w     84.00 110.00   0.50    0.14    --   79.75  16.00  77.66   52
 41  \w     38.00 100.00   0.50    0.14    --   62.87  15.00  90.00  124
 42  \w     78.00 105.00   0.50    0.14    --   79.75  13.00 167.96   54
 43  \w     57.00 108.00   0.50    0.14    --   62.87  15.00  60.00  102
 44  \w     32.00 107.00   0.50    0.14    --   62.87  15.00-150.00  150
 45  \w     55.00  80.00   0.50    0.14    --   79.75  14.00  71.91   50
 46  \w     26.00  83.00   0.50    0.14    --   62.87   0.00 150.00  114
 47  \w   -111.00 -86.00   0.50    0.14    --  -78.25 -82.00 148.87   50
 48  \w   -104.00 -79.00   0.50    0.14    --  -76.59-162.00  33.00   50
 49  \w   -103.00 -78.00   0.50    0.14    --  -73.66-162.00  33.00   50
 50  \w    -80.00 -54.00   0.50    0.14    --  -63.67-162.00  33.00   52
 51  \w   -108.00 -83.00   0.50    0.14    --  -78.25 -85.00 143.63   50
 52  \w   -113.00 -88.00   0.50    0.14    --  -78.25 -83.00 125.69   50
 53  \w   -107.00 -80.00   0.50    0.14    --  -78.25 -83.00 119.84   54
 54  \w   -106.00 -79.00   0.50    0.14    --  -78.25 -87.00  -6.83   54
 55  \w   -111.00 -85.00   0.50    0.14    --  -78.25 -91.00 -47.03   52
 56  \w   -114.00 -89.00   0.50    0.14    --  -78.25 -88.00-158.68   50
 57  \w   -110.00 -84.00   0.50    0.14    --  -78.25 -80.00-169.67   52
 58  \w   -118.00 -91.00   0.50    0.14    --  -78.25 -64.00 -13.49   54
 59  \w   -110.00 -85.00   0.50    0.14    --  -78.25 -75.00 152.24   50
 60  \w    -61.00 -35.00   0.50    0.14    --  -78.25  56.00  21.02   52
 61  \w    -62.00 -37.00   0.50    0.14    --  -78.25  57.00  -7.15   50
 62  \w    -62.00 -37.00   0.50    0.14    --  -78.25  62.00-136.81   50
 63  \w    -79.00 -54.00   0.50    0.14    --  -78.25  87.00 -72.87   50
 64  \w   -114.00 -88.00   0.50    0.14    --  -78.25 138.00  27.42   52
 65  \w    -95.00 -70.00   0.50    0.14    --  -63.67 162.00  60.00   50
 66  \w   -103.00 -77.00   0.50    0.14    --  -78.25 136.00 146.11   52
 67  \w   -118.00 -73.00   0.50    0.14    --  -73.66 162.00  60.00   90
 68  \w   -110.00 -67.00   0.50    0.14    --  -78.25 133.00 161.81   86
 69  \w   -107.00 -82.00   0.50    0.14    --  -76.59 162.00  60.00   50
 70  \w   -107.00 -60.00   0.50    0.14    --  -78.25 127.00 148.45   94
 71  \w    -75.00 -48.00   0.50    0.14    --  -78.25 138.00  27.42   54
 72  \w   -100.00 -72.00   0.50    0.14    --  -78.25 125.00 103.47   56
 73  \w   -100.00 -74.00   0.50    0.14    --  -78.25 125.00 -49.86   52
 74  \w   -107.00 -81.00   0.50    0.14    --  -78.25 127.00-105.62   52
 75  \w   -111.00 -85.00   0.50    0.14    --  -78.25 134.00-169.42   52
 76  \w    -81.00 -55.00   0.50    0.14    --  -78.25 134.00-169.42   52
 77  \w    -62.00 -32.00   0.50    0.14    --  -73.66 125.00 -60.00   60
 78  \w    -98.00 -72.00   0.50    0.14    --  -73.66 125.00 -60.00   52
 79  \w   -100.00 -74.00   0.50    0.14    --  -73.66 125.00  30.00   52
 80  \w    -89.00 -53.00   0.50    0.14    --  -63.67 125.00 150.00   72
 81  \w   -104.00 -64.00   0.50    0.14    --  -78.25 123.00  85.75   80
 82  \w    -92.00 -40.00   0.50    0.14    --  -78.25 113.00 133.71  104
 83  \w    -64.00 -34.00   0.50    0.14    --  -73.66 125.00  30.00   60
 84  \w    -67.00 -42.00   0.50    0.14    --  -78.25  96.00   4.23   50
 85  \w    -82.00 -34.00   0.50    0.14    --  -63.67 117.00 -89.00   96
 86  \w    -91.00 -66.00   0.50    0.14    --  -76.59 117.00 -89.00   50
 87  \w    -88.00 -63.00   0.50    0.14    --  -73.66 117.00 -89.00   50
 88  \w    -87.00 -62.00   0.50    0.14    --  -78.25  95.00-179.04   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      0.0160692000
_diffrn_orient_matrix_UB_12      0.0696660000
_diffrn_orient_matrix_UB_13      0.0513401000
_diffrn_orient_matrix_UB_21      -0.0111836000
_diffrn_orient_matrix_UB_22      -0.0614892000
_diffrn_orient_matrix_UB_23      0.0551419000
_diffrn_orient_matrix_UB_31      0.1681333000
_diffrn_orient_matrix_UB_32      -0.0048018000
_diffrn_orient_matrix_UB_33      0.0108931000
_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  0.0351
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            80251
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.129
_diffrn_reflns_theta_min         2.669
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.336
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.141
_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 brownish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             1448
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/n-hexane'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.065
_refine_diff_density_min         -0.764
_refine_diff_density_rms         0.075
_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     695
_refine_ls_number_reflns         12537
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0510P)^2^+1.7923P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0795
_refine_ls_wR_factor_ref         0.0803
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11791
_reflns_number_total             12537
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01229a2.cif
_cod_data_source_block           fg140_p1_
_cod_database_code               1577050
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C60 H60 Fe2 O4 P8 Sn2'
_shelx_estimated_absorpt_t_max   0.403
_shelx_estimated_absorpt_t_min   0.102
_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 Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S),
 C00Z(H00Z), C010(H010), C012(H012), C016(H016), C018(H018), C019(H019),
 C01D(H01D), C01E(H01E), C01F(H01F), C01G(H01G), C01J(H01W), C01K(H01X),
 C01L(H01Y), C01M(H01Z), C01Q(H1), C01R(H2), C01S(H3), C01U(H4), C01W(H6),
 C01Y(H7), C01Z(H8), C021(H021), C022(H022), C024(H024)
2.b Idealised Me refined as rotating group:
 C01C(H01A,H01B,H01C), C01I(H01T,H01U,H01V), C01N(H01H,H01I,H01J), C01O(H01,H,
 HA), C01P(H01K,H01L,H01M), C01T(H01N,H01O,H01P), C01V(H5,HB,HC), C01X(H01Q,
 H01R,H01S), C020(H02A,H02B,H02C), C023(H02D,H02E,H02F)
;
_shelx_res_checksum              22359
_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 1.967
_oxdiff_exptl_absorpt_empirical_full_min 0.690