A diazadiphospholenium cation featuring a reactive PP bond: synthesis and reversible main-group bond activation.
Wieneke, Jan; Cirigliano, Francesco; Schorpp, Marcel; Chemical communications (Cambridge, England) 61 (2025) 17601–17604; doi:10.1039/d5cc04820f

data_7135029
_publ_section_title
;
 A diazadiphospholenium cation featuring a reactive P&#xe006;P bond:
 synthesis and reversible main-group bond activation.
;
_journal_issue                   90
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              17601
_journal_page_last               17604
_journal_paper_doi               10.1039/d5cc04820f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C44 H51 N2 P Se2'
_chemical_formula_sum            'C44 H51 N2 P Se2'
_chemical_formula_weight         796.75
_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             2025-08-13
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-08-13 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                82.912(2)
_cell_angle_beta                 80.297(2)
_cell_angle_gamma                71.160(2)
_cell_formula_units_Z            2
_cell_length_a                   9.8450(2)
_cell_length_b                   10.4186(3)
_cell_length_c                   21.0183(5)
_cell_measurement_reflns_used    12755
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      75.0720
_cell_measurement_theta_min      4.2430
_cell_volume                     2005.68(9)
_computing_cell_refinement       'CrysAlisPro 1.171.44.100a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.100a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.100a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (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 0.996
_diffrn_measured_fraction_theta_max 0.975
_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     56.00  82.00   0.50    0.85    --   62.91-150.00 161.00   52
  2  \w     34.00  60.00   0.50    0.85    --   62.91-123.00 -35.00   52
  3  \w    -91.00 -66.00   0.50    0.85    --  -63.77 150.00-153.00   50
  4  \w    -73.00 -48.00   0.50    0.85    --  -63.77 123.00  44.00   50
  5  \w   -100.00 -59.00   0.50    0.85    --  -63.77-150.00 161.00   82
  6  \w    -91.00 -65.00   0.50    0.85    --  -73.68 123.00  44.00   52
  7  \w   -117.00 -92.00   0.50    0.85    --  -73.68 150.00-153.00   50
  8  \w     44.00  69.00   0.50    0.85    --   75.92-123.00 -35.00   50
  9  \w     54.00  79.00   0.50    0.85    --   75.92-150.00 161.00   50
 10  \w     62.00  87.00   0.50    0.85    --   75.92 150.00-153.00   50
 11  \w    -93.00 -68.00   0.50    0.85    --  -76.61 123.00  44.00   50
 12  \w   -110.00 -85.00   0.50    0.85    --  -76.61-150.00 161.00   50
 13  \w   -103.00 -78.00   0.50    0.85    --  -76.61 150.00-153.00   50
 14  \w     35.00  87.00   0.50    0.85    --   62.91   0.00-120.00  104
 15  \w     25.00  71.00   0.50    0.85    --   62.91 -95.00  30.00   92
 16  \w     26.00  98.00   0.50    0.85    --   62.91   0.00 120.00  144
 17  \w     29.00  66.00   0.50    0.85    --   62.91 -95.00-150.00   74
 18  \w     29.00  64.00   0.50    0.85    --   62.91 -95.00 -30.00   70
 19  \w    -61.00 -35.00   0.50    0.85    --  -63.77   0.00-120.00   52
 20  \w    -81.00 -36.00   0.50    0.85    --  -63.77 125.00   0.00   90
 21  \w    -87.00 -37.00   0.50    0.85    --  -63.77 125.00 120.00  100
 22  \w   -101.00 -71.00   0.50    0.85    --  -63.77   0.00-120.00   60
 23  \w    -66.00 -37.00   0.50    0.85    --  -73.68 125.00  90.00   58
 24  \w   -100.00 -34.00   0.50    0.85    --  -73.68 125.00-180.00  132
 25  \w     45.00  71.00   0.50    0.85    --   75.92  15.00  30.00   52
 26  \w     76.00 115.00   0.50    0.85    --   75.92  15.00  30.00   78
 27  \w    -83.00 -57.00   0.50    0.85    --  -78.25 139.00 -56.23   52
 28  \w   -115.00 -90.00   0.50    0.85    --  -78.25 139.00 -56.23   50
 29  \w    -61.00 -36.00   0.50    0.85    --  -78.25 136.00 134.87   50
 30  \w    -89.00 -63.00   0.50    0.85    --  -78.25 112.00 -37.61   52
 31  \w    -75.00 -49.00   0.50    0.85    --  -78.25 135.00  68.28   52
 32  \w   -122.00 -96.00   0.50    0.85    --  -78.25 -36.00-136.07   52
 33  \w    -89.00 -63.00   0.50    0.85    --  -78.25 119.00 173.31   52
 34  \w    -85.00 -59.00   0.50    0.85    --  -78.25 125.00 106.20   52
 35  \w   -109.00 -84.00   0.50    0.85    --  -78.25 -90.00 154.97   50
 36  \w   -126.00 -92.00   0.50    0.85    --  -78.25 -30.00  29.46   68
 37  \w   -105.00 -79.00   0.50    0.85    --  -78.25 -86.00 -62.00   52
 38  \w   -104.00 -79.00   0.50    0.85    --  -78.25 -90.00 130.95   50
 39  \w    -91.00 -60.00   0.50    0.85    --  -78.25 130.00-114.33   62
 40  \w   -102.00 -76.00   0.50    0.85    --  -78.25 130.00 131.25   52
 41  \w   -113.00 -87.00   0.50    0.85    --  -78.25 136.00 134.87   52
 42  \w    -76.00 -50.00   0.50    0.85    --  -78.25 117.00-167.46   52
 43  \w    -70.00 -38.00   0.50    0.85    --  -78.25 116.00-154.13   64
 44  \w    -89.00 -64.00   0.50    0.85    --  -78.25 115.00-120.46   50
 45  \w   -115.00 -84.00   0.50    0.85    --  -78.25 139.00-161.40   62
 46  \w    -85.00 -47.00   0.50    0.85    --  -78.25 122.00 165.88   76
 47  \w   -107.00 -82.00   0.50    0.85    --  -78.25 127.00 179.71   50
 48  \w   -103.00 -78.00   0.50    0.85    --  -78.25 134.00   8.97   50
 49  \w   -117.00 -92.00   0.50    0.85    --  -78.25 -48.00   9.36   50
 50  \w    -69.00 -43.00   0.50    0.85    --  -78.25 125.00   3.23   52
 51  \w    -79.00 -43.00   0.50    0.85    --  -78.25  96.00  17.30   72
 52  \w    -84.00 -59.00   0.50    0.85    --  -78.25 113.00 -52.84   50
 53  \w    -82.00 -56.00   0.50    0.85    --  -78.25 136.00 -91.34   52
 54  \w   -105.00 -79.00   0.50    0.85    --  -78.25 125.00   3.23   52
 55  \w   -111.00 -85.00   0.50    0.85    --  -78.25 134.00 178.48   52
 56  \w   -107.00 -82.00   0.50    0.85    --  -78.25 -82.00  29.08   50
 57  \w   -112.00 -86.00   0.50    0.85    --  -78.25 135.00  68.28   52
 58  \w    -88.00 -62.00   0.50    0.85    --  -78.25 113.00 103.59   52
 59  \w   -115.00 -56.00   0.50    0.85    --  -78.25 142.00-106.75  118
 60  \w    -70.00 -41.00   0.50    0.85    --  -78.25  72.00 176.97   58
 61  \w    -94.00 -69.00   0.50    0.85    --  -78.25 117.00-131.73   50
 62  \w    -96.00 -60.00   0.50    0.85    --  -78.25 122.00  32.86   72
 63  \w   -111.00 -86.00   0.50    0.85    --  -78.25 -69.00-152.02   50
 64  \w    -65.00 -40.00   0.50    0.85    --  -78.25  60.00-135.42   50
 65  \w    -76.00 -50.00   0.50    0.85    --  -78.25 117.00 -23.48   52
 66  \w    -68.00 -41.00   0.50    0.85    --  -78.25  62.00   5.84   54
 67  \w   -103.00 -77.00   0.50    0.85    --  -78.25 122.00 120.56   52
 68  \w   -120.00 -86.00   0.50    0.85    --  -78.25 147.00-139.74   68
 69  \w   -105.00 -80.00   0.50    0.85    --  -78.25 134.00  43.77   50
 70  \w     90.00 120.00   0.50    0.85    --   79.75  22.00-143.47   60
 71  \w     48.00  80.00   0.50    0.85    --   79.75  18.00 155.12   64
 72  \w     40.00  76.00   0.50    0.85    --   79.75  -4.00 144.02   72
 73  \w     92.00 117.00   0.50    0.85    --   79.75   1.00-170.23   50
 74  \w     64.00  89.00   0.50    0.85    --   79.75  22.00 -14.47   50
 75  \w     50.00  78.00   0.50    0.85    --   79.75   1.00-170.23   56
 76  \w     68.00  94.00   0.50    0.85    --   79.75  21.00 -83.22   52
 77  \w     80.00 113.00   0.50    0.85    --   79.75  22.00 -61.40   66
 78  \w     66.00 103.00   0.50    0.85    --   79.75  22.00  67.84   74
 79  \w     66.00  92.00   0.50    0.85    --   79.75  23.00 176.33   52
 80  \w     48.00 102.00   0.50    0.85    --   79.75-118.00 131.80  108
 81  \w     53.00  97.00   0.50    0.85    --   79.75  14.00  31.02   88
 82  \w     49.00 122.00   0.50    0.85    --   79.75  10.00 105.41  146
 83  \w     90.00 121.00   0.50    0.85    --   79.75   6.00-152.22   62
 84  \w     61.00  87.00   0.50    0.85    --   79.75   6.00-152.22   52
 85  \w     77.00 103.00   0.50    0.85    --   79.75  21.00-113.18   52
 86  \w     71.00 110.00   0.50    0.85    --   79.75  22.00  21.47   78
 87  \w     67.00 101.00   0.50    0.85    --   79.75  22.00-161.46   68
;
_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      -0.0063925000
_diffrn_orient_matrix_UB_12      -0.0116573000
_diffrn_orient_matrix_UB_13      0.0741581000
_diffrn_orient_matrix_UB_21      -0.0630044000
_diffrn_orient_matrix_UB_22      -0.1189354000
_diffrn_orient_matrix_UB_23      0.0050349000
_diffrn_orient_matrix_UB_31      0.1544346000
_diffrn_orient_matrix_UB_32      -0.1013055000
_diffrn_orient_matrix_UB_33      -0.0059199000
_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  0.0622
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            48190
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.503
_diffrn_reflns_theta_min         4.280
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.913
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.100a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.948
_refine_diff_density_min         -0.890
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         8100
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0456
_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^)+(0.0847P)^2^+0.5317P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1268
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6865
_reflns_number_total             8100
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           exp_6143_auto
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135029
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N P Se'
_diffrn_oxdiff_digest_hkl
;
43e35ca1f86b90f0599a9379083c00a0005ea7
;
_diffrn_oxdiff_digest_od_ed
;

;
_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:
 C18(H18), C30(H30), C15(H15), C27(H27)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C40(H40), C44(H44), C41(H41), C4(H4), C7(H7), C11(H11), C6(H6),
 C43(H43), C34(H34), C42(H42), C13(H13), C38(H38), C12(H12), C25(H25), C23(H23),
  C36(H36), C35(H35), C24(H24), C37(H37)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C31(H31A,H31B,H31C), C8(H8A,H8B,
 H8C), C28(H28A,H28B,H28C), C16(H16A,H16B,H16C), C29(H29A,H29B,H29C), C32(H32A,
 H32B,H32C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              22274
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_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 2.037
_oxdiff_exptl_absorpt_empirical_full_min 0.484