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_1576673
_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         'C76 H99 Li O, 2(C7 H8)'
_chemical_formula_sum            'C90 H115 Li O'
_chemical_formula_weight         1219.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_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                 93.8228(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.50871(7)
_cell_length_b                   29.33042(12)
_cell_length_c                   20.62954(9)
_cell_measurement_reflns_used    53833
_cell_measurement_temperature    99.95(18)
_cell_measurement_theta_max      75.2430
_cell_measurement_theta_min      2.1300
_cell_volume                     7551.84(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (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      99.95(18)
_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 0.999
_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     -8.00  17.00   0.50    1.05    --   -6.75  29.00  47.00   50
  2  \w    -58.00 -18.00   0.50    1.05    --   -6.75 -29.00-113.00   80
  3  \w     55.00  88.00   0.50    1.05    --   57.12  29.00  47.00   66
  4  \w      4.00  29.00   0.50    1.05    --   57.12 -29.00-113.00   50
  5  \w     79.00 116.00   0.50    1.05    --   69.95  29.00  47.00   74
  6  \w     83.00 108.00   0.50    1.05    --   84.10  29.00  47.00   50
  7  \w     16.00  41.00   0.50    1.05    --   57.12 -77.00-180.00   50
  8  \w     19.00  50.00   0.50    1.05    --   57.12 -61.00 -90.00   62
  9  \w     17.00  51.00   0.50    1.05    --   57.12 -61.00 -60.00   68
 10  \w      4.00  33.00   0.50    1.05    --   57.12 -30.00  60.00   58
 11  \w      4.00  29.00   0.50    1.05    --   57.12 -30.00  30.00   50
 12  \w     20.00  53.00   0.50    1.05    --   69.95 -45.00  30.00   66
 13  \w     32.00  73.00   0.50    1.05    --   69.95 -95.00 120.00   82
 14  \w     22.00  51.00   0.50    1.05    --   69.95 -45.00 150.00   58
 15  \w     21.00  53.00   0.50    1.05    --   69.95 -45.00 120.00   64
 16  \w     21.00  53.00   0.50    1.05    --   69.95 -45.00  90.00   64
 17  \w     76.00 102.00   0.50    1.05    --   84.10-111.00-120.00   52
 18  \w     92.00 123.00   0.50    1.05    --   84.10  45.00   0.00   62
 19  \w    101.00 135.00   0.50    1.05    --   84.10  45.00-180.00   68
 20  \w     62.00  98.00   0.50    1.05    --   84.10 -95.00 120.00   72
 21  \w     38.00  64.00   0.50    1.05    --   84.10 -61.00 -90.00   52
 22  \w     42.00  68.00   0.50    1.05    --   84.10-111.00-120.00   52
 23  \w     51.00  77.00   0.50    1.05    --   84.10 -77.00 120.00   52
 24  \w     44.00  70.00   0.50    1.05    --   84.10 -77.00 -30.00   52
 25  \w     58.00  84.00   0.50    1.05    --   84.10 -77.00  90.00   52
 26  \w     37.00  62.00   0.50    1.05    --   84.10 -61.00   0.00   50
 27  \w     42.00  67.00   0.50    1.05    --   84.10 -61.00 -30.00   50
 28  \w     37.00  62.00   0.50    1.05    --   84.10 -61.00  30.00   50
 29  \w     43.00  68.00   0.50    1.05    --   84.10 -77.00-150.00   50
 30  \w     93.00 119.00   0.50    1.05    --   84.10  45.00-120.00   52
 31  \w     91.00 135.00   0.50    1.05    --   84.10  45.00-150.00   88
 32  \w    102.00 128.00   0.50    1.05    --   84.10  45.00 150.00   52
 33  \w     37.00  62.00   0.50    1.05    --   84.10 -61.00 150.00   50
 34  \w    103.00 134.00   0.50    1.05    --   84.10  30.00-180.00   62
 35  \w     46.00  95.00   0.50    1.05    --   86.75-108.00 -86.14   98
 36  \w     48.00 127.00   0.50    1.05    --   86.75   8.00 171.72  158
 37  \w     51.00  97.00   0.50    1.05    --   86.75 -96.00 165.29   92
 38  \w    116.00 141.00   0.50    1.05    --   86.75  25.00 168.29   50
 39  \w     86.00 112.00   0.50    1.05    --   86.75  25.00 168.29   52
 40  \w     63.00 105.00   0.50    1.05    --   86.75  24.00 -13.57   84
 41  \w     65.00 134.00   0.50    1.05    --   86.75  23.00  87.07  138
 42  \w     99.00 124.00   0.50    1.05    --   86.75  12.00  40.76   50
 43  \w     51.00  95.00   0.50    1.05    --   86.75  12.00  40.76   88
 44  \w     49.00 102.00   0.50    1.05    --   86.75-107.00  65.84  106
 45  \w     73.00 113.00   0.50    1.05    --   86.75   1.00 134.53   80
 46  \w     45.00  90.00   0.50    1.05    --   86.75 -97.00  92.95   90
 47  \w     42.00  68.00   0.50    1.05    --   86.75 -63.00 111.81   52
 48  \w     -8.00  17.00   0.50    1.05    --   -6.75  29.00  47.00   50
 49  \w    -14.00  12.00   0.50    1.05    --   -6.75-100.00 147.95   52
 50  \w     -2.00  28.00   0.50    1.05    --   -6.75  61.00 -90.00   60
 51  \w     -3.00  22.00   0.50    1.05    --   -6.75  61.00  60.00   50
 52  \w     -2.00  29.00   0.50    1.05    --   -6.75  61.00-180.00   62
 53  \w     -5.00  21.00   0.50    1.05    --   10.00  94.00 -56.11   52
 54  \w     -4.00  21.00   0.50    1.05    --   14.00 100.00 144.64   50
 55  \w     17.00  42.00   0.50    1.05    --   22.00  79.00  69.54   50
 56  \w     16.00  41.00   0.50    1.05    --   26.00  87.00 106.21   50
 57  \w     14.00  39.00   0.50    1.05    --   26.00  91.00-123.48   50
 58  \w     14.00  39.00   0.50    1.05    --   26.00  91.00  65.55   50
 59  \w     15.00  40.00   0.50    1.05    --   26.00  89.00 -76.27   50
 60  \w     16.00  41.00   0.50    1.05    --   26.00  88.00 -13.15   50
 61  \w     13.00  38.00   0.50    1.05    --   26.00  92.00 155.72   50
 62  \w     31.00  56.00   0.50    1.05    --   34.00  77.00  29.97   50
 63  \w     32.00  57.00   0.50    1.05    --   34.00  75.00-177.93   50
 64  \w     31.00  56.00   0.50    1.05    --   34.00  77.00 136.75   50
 65  \w     31.00  56.00   0.50    1.05    --   34.00  77.00 -91.57   50
 66  \w     35.00  60.00   0.50    1.05    --   38.00  77.00-170.04   50
 67  \w     35.00  49.50   0.50    1.05    --   38.00  77.00-151.20   29
;
_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      0.0289809000
_diffrn_orient_matrix_UB_12      0.0162998000
_diffrn_orient_matrix_UB_13      -0.0675943000
_diffrn_orient_matrix_UB_21      0.1189095000
_diffrn_orient_matrix_UB_22      -0.0105387000
_diffrn_orient_matrix_UB_23      0.0180945000
_diffrn_orient_matrix_UB_31      -0.0161016000
_diffrn_orient_matrix_UB_32      -0.0487961000
_diffrn_orient_matrix_UB_33      -0.0265825000
_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  0.0244
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            113737
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         2.623
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.449
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.073
_exptl_crystal_description       block
_exptl_crystal_F_000             2664
_exptl_crystal_size_max          0.233
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.538
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1032
_refine_ls_number_reflns         13460
_refine_ls_number_restraints     576
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0623
_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^)+(0.0646P)^2^+5.8271P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1567
_refine_ls_wR_factor_ref         0.1597
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12234
_reflns_number_total             13460
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_2
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_database_code               1576673
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C79 H101 Li'
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.903
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C58-C59 \\sim C58-C59A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60A
 with sigma of 0.02
 C60-C61 \\sim C60A-C61
 with sigma of 0.02
 C58-C60 \\sim C58-C60A
 with sigma of 0.04
 C59-C61 \\sim C59A-C61
 with sigma of 0.04
 C80-C81 \\sim C80A-C81A
 with sigma of 0.02
 C80-C85 \\sim C80A-C85A
 with sigma of 0.02
 C80-C86 \\sim C80A-C86A
 with sigma of 0.02
 C81-C82 \\sim C81A-C82A
 with sigma of 0.02
 C82-C83 \\sim C82A-C83A
 with sigma of 0.02
 C83-C84 \\sim C83A-C84A
 with sigma of 0.02
 C84-C85 \\sim C84A-C85A
 with sigma of 0.02
 C80-C82 \\sim C80A-C82A
 with sigma of 0.04
 C80-C84 \\sim C80A-C84A
 with sigma of 0.04
 C81-C83 \\sim C81A-C83A
 with sigma of 0.04
 C81-C85 \\sim C81A-C85A
 with sigma of 0.04
 C81-C86 \\sim C81A-C86A
 with sigma of 0.04
 C82-C84 \\sim C82A-C84A
 with sigma of 0.04
 C83-C85 \\sim C83A-C85A
 with sigma of 0.04
 C85-C86 \\sim C85A-C86A
 with sigma of 0.04
 C77-C78 \\sim C77A-C78A
 with sigma of 0.02
 C77-C76 \\sim C77A-C76A
 with sigma of 0.02
 C74-C73 \\sim C74A-C73A
 with sigma of 0.02
 C74-C75 \\sim C74A-C75A
 with sigma of 0.02
 C73-C78 \\sim C73A-C78A
 with sigma of 0.02
 C73-C79 \\sim C73A-C79A
 with sigma of 0.02
 C76-C75 \\sim C76A-C75A
 with sigma of 0.02
 C77-C73 \\sim C77A-C73A
 with sigma of 0.04
 C77-C75 \\sim C77A-C75A
 with sigma of 0.04
 C74-C78 \\sim C74A-C78A
 with sigma of 0.04
 C74-C76 \\sim C74A-C76A
 with sigma of 0.04
 C74-C79 \\sim C74A-C79A
 with sigma of 0.04
 C73-C75 \\sim C73A-C75A
 with sigma of 0.04
 C78-C76 \\sim C78A-C76A
 with sigma of 0.04
 C78-C79 \\sim C78A-C79A
 with sigma of 0.04
 C30-C31 \\sim C30-C31A
 with sigma of 0.02
 C30-C43 \\sim C30-C43A
 with sigma of 0.02
 C30-C44 \\sim C30-C44A
 with sigma of 0.02
 C32-C31 \\sim C32-C31A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C77A \\sim C79A \\sim C73A \\sim C74A \\sim C78A \\sim C75A \\sim C76A \\sim
C78 \\sim C77 \\sim C76 \\sim C73 \\sim C75 \\sim C74 \\sim C79: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C44A \\sim C44 \\sim C43A \\sim C43 \\sim C30 \\sim C31 \\sim C31A \\sim C32
\\sim C33: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Rigid body (RIGU) restrains
 C80, C81, C82, C83, C84, C85, C86
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77A, C79A, C73A, C74A, C78A, C75A, C76A, C73, C77, C78, C76, C75, C74, C79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44A, C44, C43A, C43, C30, C31, C31A, C32, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60C)=Sof(H60D)=1-FVAR(1)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=FVAR(1)
 Sof(C86A)=Sof(H86D)=Sof(H86E)=Sof(H86F)=Sof(C80A)=Sof(C81A)=Sof(H81A)=
 Sof(C82A)=Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=
 Sof(H85A)=1-FVAR(2)
 Sof(C80)=Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83)=Sof(C84)=
 Sof(H84)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=FVAR(2)
 Sof(C79A)=Sof(H79D)=Sof(H79E)=Sof(H79F)=Sof(C73A)=Sof(C78A)=Sof(H78A)=
 Sof(C77A)=Sof(H77A)=Sof(C76A)=Sof(H76A)=Sof(C75A)=Sof(H75A)=Sof(C74A)=
 Sof(H74A)=1-FVAR(3)
 Sof(C77)=Sof(H77)=Sof(C74)=Sof(H74)=Sof(C73)=Sof(C78)=Sof(H78)=Sof(C76)=
 Sof(H76)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C75)=Sof(H75)=FVAR(3)
 Sof(H32C)=Sof(H32D)=Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(C44A)=Sof(H44D)=
 Sof(H44E)=Sof(H44F)=Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=1-FVAR(4)
 Sof(H32A)=Sof(H32B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C89(H89A,H89B), C4(H4A,H4B), C10(H10A,H10B), C88(H88A,H88B), C21(H21A,H21B),
 C22(H22A,H22B), C49(H49A,H49B), C50(H50A,H50B), C59(H59A,H59B), C60(H60A,H60B),
  C59A(H59C,H59D), C60A(H60C,H60D), C32(H32A,H32B), C32(H32C,H32D), C31(H31A,
 H31B), C31A(H31C,H31D)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C18(H18), C25(H25), C28(H28), C35(H35), C46(H46), C53(H53), C56(H56),
 C63(H63), C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C81A(H81A),
 C82A(H82A), C83A(H83A), C84A(H84A), C85A(H85A), C77(H77), C74(H74), C78(H78),
 C76(H76), C75(H75), C78A(H78A), C77A(H77A), C76A(H76A), C75A(H75A), C74A(H74A)
6.c Idealised Me refined as rotating group:
 C87(H87A,H87B,H87C), C90(H90A,H90B,H90C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C86(H86A,H86B,H86C), C86A(H86D,H86E,H86F),
 C79(H79A,H79B,H79C), C79A(H79D,H79E,H79F), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C44A(H44D,H44E,H44F), C43A(H43D,H43E,H43F)
;
_shelx_res_checksum              64776
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.838