Isolation of arylhalodiphosphenes: periodic trends in R–PP–X bonding (X = Cl, Br, I)
Wenger, John S.; Gaschik, Nina; Rowe, William J.; Crumpton, Agamemnon E.; van IJzendoorn, Bono; Mehta, Meera; Chemical Science  (2026) –; doi:10.1039/D6SC00723F

data_1576681
_publ_section_title
;
 Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond,
 length as m-dash]P-X bonding (X = Cl, Br, I).
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              7475
_journal_page_last               7485
_journal_paper_doi               10.1039/d6sc00723f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C75 H99 P Si, 2(C4 H10 O)'
_chemical_formula_sum            'C83 H119 O2 P Si'
_chemical_formula_weight         1207.83
_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_Hall           'P -4 2ab'
_space_group_name_H-M_alt        'P -4 21 m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-29
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2026-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.70963(15)
_cell_length_b                   17.70963(15)
_cell_length_c                   11.8110(2)
_cell_measurement_reflns_used    29414
_cell_measurement_temperature    149.97(13)
_cell_measurement_theta_max      76.1700
_cell_measurement_theta_min      4.4190
_cell_volume                     3704.30(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.97(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      5.00  37.00   1.00    1.00    --  -41.77  19.00   0.00   32
  2  \w     -5.00  35.00   1.00    1.00    --  -41.77  19.00 -30.00   40
  3  \w      5.00  31.00   1.00    1.00    --  -41.77  37.00-120.00   26
  4  \w     -2.00  35.00   1.00    1.00    --  -41.77  19.00 120.00   37
  5  \w    -19.00  24.00   1.00    1.00    --  -41.77  37.00  90.00   43
  6  \w     -4.00  30.00   1.00    1.00    --  -41.77  19.00-120.00   34
  7  \w      1.00  37.00   1.00    1.00    --  -41.77  19.00  30.00   36
  8  \w    -38.00  10.00   1.00    1.00    --  -41.77  57.00-180.00   48
  9  \w     38.00  81.00   1.00    1.00    --   41.77 -99.00-150.00   43
 10  \w     32.00  75.00   1.00    1.00    --   41.77-125.00   0.00   43
 11  \w     36.00  83.00   1.00    1.00    --   41.77-125.00 120.00   47
 12  \w     44.00  91.00   1.00    3.17    --  111.00-125.00  30.00   47
 13  \w    117.00 166.00   1.00    3.17    --  111.00  77.00-180.00   49
 14  \w     48.00  88.00   1.00    3.17    --  111.00-125.00 -30.00   40
 15  \w     41.00 112.00   1.00    3.17    --  111.00-125.00  60.00   71
 16  \w     62.00  88.00   1.00    3.17    --  111.00 -61.00-150.00   26
 17  \w    112.00 176.00   1.00    3.17    --  111.00  77.00  90.00   64
 18  \w    124.00 178.00   1.00    3.17    --  111.00  77.00 -30.00   54
 19  \w     70.00 112.00   1.00    3.17    --  111.00-125.00  90.00   42
 20  \w     99.00 130.00   1.00    3.17    --  111.00 125.00-150.00   31
 21  \w     63.00 112.00   1.00    3.17    --  111.00-125.00   0.00   49
 22  \w     33.00 107.00   1.00    3.17    --  111.00 -94.00 150.00   74
 23  \w     42.00  72.00   1.00    3.17    --  111.00 -45.00  60.00   30
 24  \w    115.00 175.00   1.00    3.17    --  111.00  15.00 150.00   60
 25  \w     41.00  67.00   1.00    3.17    --  111.00 -45.00 -60.00   26
 26  \w     69.00 100.00   1.00    3.17    --  111.00  15.00 150.00   31
 27  \w     56.00 107.00   1.00    3.17    --  111.00 -94.00  90.00   51
 28  \w     91.00 147.00   1.00    3.17    --  111.00  45.00 -90.00   56
 29  \w     47.00 107.00   1.00    3.17    --  111.00 -94.00  60.00   60
 30  \w     80.00 107.00   1.00    3.17    --  111.00 -94.00-120.00   27
 31  \w     59.00  85.00   1.00    3.17    --  111.00 -61.00 150.00   26
 32  \w     66.00 107.00   1.00    3.17    --  111.00 -94.00 -30.00   41
 33  \w     41.00  66.00   1.00    3.17    --  111.00 -61.00   0.00   25
 34  \w     74.00 100.00   1.00    3.17    --  111.00-125.00 150.00   26
 35  \w     80.00 107.00   1.00    3.17    --  111.00 -94.00-180.00   27
 36  \w     32.00  75.00   1.00    3.17    --  111.00 -94.00-180.00   43
 37  \w     90.00 120.00   1.00    3.17    --  111.00  45.00  30.00   30
 38  \w    148.00 174.00   1.00    3.17    --  111.00  45.00  30.00   26
 39  \w     42.00 110.00   1.00    3.17    --  111.00-125.00 -90.00   68
 40  \w     41.00  71.00   1.00    3.17    --  111.00 -45.00  30.00   30
 41  \w    122.00 149.00   1.00    3.17    --  111.00 125.00 -90.00   27
 42  \w    105.00 177.00   1.00    3.17    --  111.00  77.00  30.00   72
 43  \w      2.00  27.00   1.00    1.00    --   38.00  90.00 -86.79   25
 44  \w      6.00  33.00   1.00    1.00    --   38.00  78.00  97.12   27
 45  \w   -102.00 -49.00   1.00    1.00    --  -41.77 -57.00  60.00   53
 46  \w     -1.00  28.00   1.00    1.00    --  -41.77  19.00  60.00   29
 47  \w    -73.00 -19.00   1.00    1.00    --  -41.77 -37.00 -60.00   54
 48  \w    -45.00 -15.00   1.00    1.00    --  -41.77 -57.00  60.00   30
 49  \w   -115.00 -75.00   1.00    1.00    --  -41.77 -37.00 -60.00   40
 50  \w     16.00  42.00   1.00    1.00    --   46.00  82.00  70.59   26
 51  \w     13.00  38.00   1.00    1.00    --   46.00  82.00 -41.77   25
 52  \w     13.00  38.00   1.00    1.00    --   46.00  82.00  27.32   25
 53  \w     14.00  40.00   1.00    1.00    --   46.00  82.00-128.92   26
 54  \w     13.00  39.00   1.00    1.00    --   46.00  82.00 159.50   26
 55  \w     32.00  61.00   1.00    1.00    --   62.00  70.00 -18.74   29
 56  \w     32.00  58.00   1.00    1.00    --   62.00  70.00 -70.95   26
 57  \w    104.00 130.00   1.00    1.00    --   62.00  70.00 -18.74   26
 58  \w     97.00 123.00   1.00    1.00    --   62.00  70.00 -70.95   26
 59  \w     36.00  62.00   1.00    1.00    --   66.00  71.00-172.27   26
 60  \w    106.00 135.00   1.00    1.00    --   66.00  71.00  59.33   29
 61  \w     38.00  75.00   1.00    1.00    --   66.00  70.00-113.94   37
 62  \w     36.00  69.00   1.00    1.00    --   66.00  71.00  59.33   33
 63  \w     41.00  71.00   1.00    1.00    --   66.00  53.00 -36.42   30
 64  \w     40.00  82.00   1.00    1.00    --   70.00  71.00-139.19   42
 65  \w     40.00  69.00   1.00    1.00    --   70.00  71.00 101.16   29
 66  \w     40.00  78.00   1.00    1.00    --   70.00  70.00 142.62   38
 67  \w     41.00  73.00   1.00    1.00    --   70.00  69.00   6.38   32
 68  \w    137.00 167.00   1.00    3.17    --  111.00  61.00 150.00   30
 69  \w     83.00 163.00   1.00    3.17    --  111.00  61.00 -60.00   80
 70  \w     83.00 134.00   1.00    3.17    --  111.00  61.00-180.00   51
 71  \w     83.00  95.00   1.00    3.17    --  111.00  61.00-150.00   12
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0360771000
_diffrn_orient_matrix_UB_12      -0.0119879000
_diffrn_orient_matrix_UB_13      0.1173270000
_diffrn_orient_matrix_UB_21      -0.0607919000
_diffrn_orient_matrix_UB_22      0.0592578000
_diffrn_orient_matrix_UB_23      -0.0283475000
_diffrn_orient_matrix_UB_31      -0.0507065000
_diffrn_orient_matrix_UB_32      -0.0625202000
_diffrn_orient_matrix_UB_33      -0.0494867000
_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  0.0452
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            62152
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.094
_diffrn_reflns_theta_min         3.529
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.810
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.083
_exptl_crystal_description       block
_exptl_crystal_F_000             1324
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.103
_refine_diff_density_max         0.355
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1637 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4054
_refine_ls_number_restraints     513
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0719P)^2^+0.2174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.795
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3829
_reflns_number_total             4054
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_6
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_original_cell_volume        3704.30(9)
_cod_database_code               1576681
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C79 O1 H109 P1 Si1'
_cell_oxdiff_angle_alpha         90.004(2)
_cell_oxdiff_angle_beta          90.036(2)
_cell_oxdiff_angle_gamma         89.9969(19)
_cell_oxdiff_length_a            17.7129(4)
_cell_oxdiff_length_b            17.7090(4)
_cell_oxdiff_length_c            11.8093(3)
_cell_oxdiff_measurement_reflns_used 27855
_cell_oxdiff_volume              3704.30(16)
_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
 C6-C11 \\sim C6-C10
 with sigma of 0.02
 C27-C26 \\sim C26-C28 \\sim C28-C27
 with sigma of 0.03
 P1-C27 \\sim P1-C26 \\sim P1-C28
 with sigma of 0.04
 C9-C1 \\sim C1-C2 \\sim C3-C2 \\sim C3-C4 \\sim C5-C4 \\sim C5-C9
 with sigma of 0.02
 C9-C3 \\sim C4-C1 \\sim C5-C2
 with sigma of 0.02
3. Restrained planarity
 C1, C2, C3, C4, C5, C9
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
P1 \\sim Si1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7
\\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15
\\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23
\\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim O1 \\sim C29 \\sim C30
\\sim C31 \\sim C32: within 2A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 2A
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C9) = Uanis(C2)
Uanis(C5) = Uanis(C3)
Uanis(C28) = Uanis(C27)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: P1(0.25) H1(0.25) Si1(0.25) C1(0.25) C2(0.25) C3(0.25) C4(0.25)
 H4(0.25) C5(0.25) C9(0.25) H7A(0.5) H7B(0.5) C11(0.5) H11A(0.5) H11B(0.5)
 H11C(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C28(0.25) H28A(0.25)
 H28B(0.25) H28C(0.25) C27(0.25) H27A(0.25) H27B(0.25) H27C(0.25) C26(0.25)
 H26A(0.25) H26B(0.25) H26C(0.25) O1(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) C31(0.5) H31A(0.5) H31B(0.5) C32(0.5)
 H32A(0.5) H32B(0.5) H32C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C16(H16A,H16B), C17(H17A,H17B), C30(H30A,H30B), C31(H31A,H31B)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C20(H20), C13(H13)
7.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C23(H23A,H23B,H23C), C22(H22A,H22B,
 H22C), C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C27(H27A,
 H27B,H27C), C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              86752
_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 1.207
_oxdiff_exptl_absorpt_empirical_full_min 0.844