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_1576675
_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         'C73 H89 Ag Cl F3 O3 P2 S, [+ solvents]'
_chemical_formula_sum            'C73 H89 Ag Cl F3 O3 P2 S'
_chemical_formula_weight         1308.76
_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             2026-01-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-01-18 deposited with the CCDC.	2026-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.3380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8885(2)
_cell_length_b                   27.6598(3)
_cell_length_c                   18.0802(2)
_cell_measurement_reflns_used    27291
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4100
_cell_measurement_theta_min      2.9790
_cell_volume                     7662.74(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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      100.00(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 0.988
_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     11.00  36.00   0.50    2.16    --   60.20 -30.00 -90.00   50
  2  \w     11.00  36.00   0.50    2.16    --   60.20 -30.00  30.00   50
  3  \w     11.00  37.00   0.50    2.16    --   60.20 -30.00  90.00   52
  4  \w     61.00  86.00   0.50    2.16    --   60.20  30.00 -90.00   50
  5  \w     28.00  61.00   0.50    2.16    --   60.20 -95.00  90.00   66
  6  \w     11.00  36.00   0.50    2.16    --   60.20 -30.00 150.00   50
  7  \w     12.00  37.00   0.50    2.16    --   60.20 -30.00  60.00   50
  8  \w     11.00  36.00   0.50    2.16    --   60.20 -30.00 120.00   50
  9  \w     65.00 106.00   0.50    2.16    --   60.20  30.00-120.00   82
 10  \w     78.00 118.00   0.50    2.16    --   73.68  30.00 -90.00   80
 11  \w     76.00 103.00   0.50    2.16    --   73.68  30.00 -30.00   54
 12  \w     35.00  99.00   0.50    2.16    --   73.68-125.00-180.00  128
 13  \w     36.00  80.00   0.50    2.16    --   73.68 -95.00 -90.00   88
 14  \w     53.00  96.00   0.50    2.16    --   79.80-125.00  60.00   86
 15  \w     62.00  88.00   0.50    2.16    --   79.80 -95.00   0.00   52
 16  \w     86.00 118.00   0.50    2.16    --   79.80  30.00-180.00   64
 17  \w     41.00  66.00   0.50    2.16    --   79.80-125.00 120.00   50
 18  \w     88.00 120.00   0.50    2.16    --   79.80  30.00 -60.00   64
 19  \w     68.00  98.00   0.50    2.16    --   82.00-103.00  65.72   60
 20  \w     93.00 129.00   0.50    2.16    --   83.00  25.00 -30.05   72
 21  \w     44.00  75.00   0.50    2.16    --   83.00-101.00-113.59   62
 22  \w     62.00 127.00   0.50    2.16    --   83.00  19.00 -91.59  130
 23  \w     65.00 113.00   0.50    2.16    --   83.00  23.00  88.83   96
 24  \w     45.00 106.00   0.50    2.16    --   83.00   4.00-168.20  122
 25  \w     49.00 127.00   0.50    2.16    --   83.00   6.00 108.50  156
 26  \w     39.00  65.00   0.50    2.16    --   83.00 -55.00 -29.17   52
 27  \w     59.00  96.00   0.50    2.16    --   83.00-108.00 -64.06   74
 28  \w     47.00  95.00   0.50    2.16    --   83.00 -99.00  46.86   96
 29  \w     93.00 119.00   0.50    2.16    --   83.00  44.00 -92.18   52
 30  \w     55.00  81.00   0.50    2.16    --   83.00  19.00-149.75   52
 31  \w     54.00  99.00   0.50    2.16    --   83.00  14.00  57.52   90
 32  \w     95.00 128.00   0.50    2.16    --   83.00  19.00-149.75   66
 33  \w     75.00 100.00   0.50    2.16    --   83.00-105.00 121.68   50
 34  \w     74.00 119.00   0.50    2.16    --   83.00  25.00 127.70   90
 35  \w     41.00  66.00   0.50    2.16    --   83.00 -64.00-176.57   50
 36  \w    -17.00   9.00   0.50    2.16    --   -3.00 -98.00-117.41   52
 37  \w    -16.00   9.00   0.50    2.16    --   -3.00-100.00 110.50   50
 38  \w    -41.00 -14.00   0.50    2.16    --   -3.00 -48.00-117.09   54
 39  \w    -15.00  11.00   0.50    2.16    --   -3.00-100.00  41.72   52
 40  \w     -6.00  19.00   0.50    2.16    --    6.00  98.00 -35.96   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      -0.0503115000
_diffrn_orient_matrix_UB_12      -0.0148413000
_diffrn_orient_matrix_UB_13      -0.0819134000
_diffrn_orient_matrix_UB_21      0.0772249000
_diffrn_orient_matrix_UB_22      -0.0320367000
_diffrn_orient_matrix_UB_23      -0.0059382000
_diffrn_orient_matrix_UB_31      -0.0402200000
_diffrn_orient_matrix_UB_32      -0.0430593000
_diffrn_orient_matrix_UB_33      0.0325964000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            90526
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.967
_diffrn_reflns_theta_min         2.996
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.456
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68734
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.134
_exptl_crystal_description       block
_exptl_crystal_F_000             2752
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.959
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     917
_refine_ls_number_reflns         15794
_refine_ls_number_restraints     731
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0688P)^2^+6.3556P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1355
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12507
_reflns_number_total             15794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_11
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_database_code               1576675
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C73 H89 P2 O3 F3 S1'
_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
 P1-P2 \\sim P1-P2A
 with sigma of 0.02
 P2-Cl1 \\sim P2A-Cl1A
 with sigma of 0.02
 P1-Cl1 \\sim P1-Cl1A
 with sigma of 0.04
 C61-C70 \\sim C61-C70A
 with sigma of 0.02
 C61-C69 \\sim C61-C69A
 with sigma of 0.02
 C61-C60 \\sim C61-C60A
 with sigma of 0.02
 C59-C60 \\sim C59-C60A
 with sigma of 0.02
 C58-C71 \\sim C58-C71A
 with sigma of 0.02
 C58-C59 \\sim C58-C59A
 with sigma of 0.02
 C58-C72 \\sim C58-C72A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60
 with sigma of 0.02
 C59-C60A \\sim C59A-C60A
 with sigma of 0.02
 C48-C49 \\sim C48-C49A
 with sigma of 0.02
 C48-C66 \\sim C48-C66A
 with sigma of 0.02
 C48-C65 \\sim C48-C65A
 with sigma of 0.02
 C50-C49 \\sim C50-C49A
 with sigma of 0.02
 C51-C67 \\sim C51-C67A
 with sigma of 0.02
 C51-C50 \\sim C51-C50A
 with sigma of 0.02
 C51-C68 \\sim C51-C68A
 with sigma of 0.02
 C50-C49 \\sim C50A-C49
 with sigma of 0.02
 C50-C49A \\sim C50A-C49A
 with sigma of 0.02
 C23-C22 \\sim C23-C22A
 with sigma of 0.02
 C20-C21 \\sim C20-C21A
 with sigma of 0.02
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C23-C21 \\sim C23-C21A
 with sigma of 0.04
 C20-C22 \\sim C20-C22A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C23 \\sim C39 \\sim C20 \\sim C51 \\sim C48 \\sim C22 \\sim C37 \\sim C50 \\sim
C21 \\sim C68 \\sim C49 \\sim C66 \\sim C65 \\sim C49A \\sim C66A \\sim C65A
\\sim C50A \\sim C21A \\sim C22A \\sim C38 \\sim C40 \\sim C67 \\sim C68A \\sim
C67A \\sim C33 \\sim C43 \\sim C32 \\sim C41 \\sim C42 \\sim C61 \\sim C59
\\sim C70 \\sim C69 \\sim C60 \\sim C60A \\sim C70A \\sim C69A \\sim C59A \\sim
C30 \\sim C31 \\sim C58 \\sim C71 \\sim C72 \\sim C71A \\sim C72A \\sim C44:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C23, C39, C20, C51, C48, C22, C37, C50, C21, C68, C49, C66, C65, C49A, C66A,
 C65A, C50A, C21A, C22A, C38, C40, C67, C68A, C67A, C33, C43, C32, C41, C42,
 C61, C59, C70, C69, C60, C60A, C70A, C69A, C59A, C30, C31, C58, C71, C72, C71A,
  C72A, C44
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(P2A)=Sof(Cl1A)=1-FVAR(1)
 Sof(P2)=Sof(Cl1)=FVAR(1)
 Sof(C60A)=Sof(H60C)=Sof(H60D)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=
 Sof(C69A)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C59A)=Sof(H59C)=Sof(H59D)=
 Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72A)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=1-FVAR(2)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C70)=
 Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C72)=
 Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C60)=Sof(H60A)=Sof(H60B)=FVAR(2)
 Sof(C49A)=Sof(H49C)=Sof(H49D)=Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=
 Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C50A)=Sof(H50C)=Sof(H50D)=
 Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C67A)=Sof(H67D)=Sof(H67E)=
 Sof(H67F)=1-FVAR(3)
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C68)=
 Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C66)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(3)
 Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=1-FVAR(4)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C21)=Sof(H21A)=Sof(H21B)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C31(H31A,H31B), C10(H10A,H10B), C32(H32A,H32B), C22(H22A,H22B),
 C50(H50A,H50B), C21(H21A,H21B), C59(H59A,H59B), C49(H49A,H49B), C60(H60A,H60B),
  C60A(H60C,H60D), C59A(H59C,H59D), C49A(H49C,H49D), C50A(H50C,H50D), C21A(H21C,
 H21D), C22A(H22C,H22D)
6.b Me refined with riding coordinates:
 C71(H71A,H71B,H71C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,
 H70C), C69(H69A,H69B,H69C), C72(H72A,H72B,H72C), C66(H66A,H66B,H66C), C65(H65A,
 H65B,H65C), C70A(H70D,H70E,H70F), C69A(H69D,H69E,H69F), C71A(H71D,H71E,H71F),
 C72A(H72D,H72E,H72F), C66A(H66D,H66E,H66F), C65A(H65D,H65E,H65F), C68A(H68D,
 H68E,H68F), C67A(H67D,H67E,H67F)
6.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C35(H35), C28(H28), C18(H18), C53(H53), C56(H56), C63(H63), C7(H7),
 C46(H46)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C44(H44A,H44B,H44C), C43(H43A,H43B,
 H43C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C38(H38A,H38B,H38C), C42(H42A,
 H42B,H42C), C40(H40A,H40B,H40C), C16(H16A,H16B,H16C), C15(H15A,H15B,H15C),
 C37(H37A,H37B,H37C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66244
_shelx_fab_checksum              35681
_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 1.385
_oxdiff_exptl_absorpt_empirical_full_min 0.711