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_7135034
_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 P2 S2, C F3 O3 S'
_chemical_formula_sum            'C45 H51 F3 N2 O3 P2 S3'
_chemical_formula_weight         883.059
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-11
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-08-13 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                94.945(1)
_cell_angle_beta                 99.955(1)
_cell_angle_gamma                94.997(1)
_cell_formula_units_Z            2
_cell_length_a                   10.4857(1)
_cell_length_b                   13.3395(1)
_cell_length_c                   16.2297(1)
_cell_measurement_reflns_used    36308
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.6090
_cell_measurement_theta_min      2.7590
_cell_volume                     2215.54(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.100a 64-bit (release 20-03-2025))'
_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  'olex2.refine 1.5 (Bourhis et al., 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 0.9971
_diffrn_measured_fraction_theta_max 0.9698
_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  21.00   0.50    0.85    --    6.00 100.00  28.70   52
  2  \w    -19.00   7.00   0.50    0.85    --   -6.00 103.00-127.92   52
  3  \w    -46.00 -21.00   0.50    0.85    --  -10.00 138.00   5.89   50
  4  \w      2.00  27.00   0.50    0.85    --   10.00  95.00  -1.37   50
  5  \w     16.00  41.00   0.50    0.85    --   18.00  85.00  87.71   50
  6  \w     13.00  38.00   0.50    0.85    --   18.00  90.00 156.26   50
  7  \w     17.00  43.00   0.50    0.85    --   22.00  90.00 -13.83   52
  8  \w     17.00  42.00   0.50    0.85    --   22.00  90.00-134.86   50
  9  \w     17.00  42.00   0.50    0.85    --   22.00  90.00-101.00   50
 10  \w     33.00  58.00   0.50    0.85    --   30.00  77.00  34.29   50
 11  \w     37.00  62.00   0.50    0.85    --   30.00  71.00 -58.42   50
 12  \w     35.00  60.00   0.50    0.85    --   30.00  74.00 -20.28   50
 13  \w     38.00  63.00   0.50    0.85    --   34.00  76.00-151.19   50
 14  \w     39.00  64.00   0.50    0.85    --   34.00  74.00 109.65   50
 15  \w     39.00  64.00   0.50    0.85    --   34.00  75.00  91.20   50
 16  \w     41.00  66.00   0.50    0.85    --   34.00  71.00 136.97   50
 17  \w     37.00  62.00   0.50    0.85    --   34.00  77.00  53.73   50
 18  \w     39.00  64.00   0.50    0.85    --   34.00  74.00-177.09   50
 19  \w     39.00  64.00   0.50    0.85    --   34.00  74.00-126.05   50
 20  \w     38.00  63.00   0.50    0.85    --   34.00  76.00 157.08   50
 21  \w     44.00  69.00   0.50    0.85    --   38.00  72.00 -22.55   50
 22  \w     43.00  68.00   0.50    0.85    --   38.00  74.00  17.80   50
 23  \w     44.00  69.00   0.50    0.85    --   38.00  73.00 -62.07   50
 24  \w     44.00  69.00   0.50    0.85    --   38.00  72.00  -2.68   50
 25  \w     42.00  67.00   0.50    0.85    --   38.00  76.00 132.77   50
 26  \w     41.00  66.00   0.50    0.85    --   38.00  77.00-110.91   50
 27  \w     48.00  73.00   0.50    0.85    --   42.00  72.00  96.99   50
 28  \w     50.00  75.00   0.50    0.85    --   42.00  68.00  58.61   50
 29  \w     51.00  76.00   0.50    0.85    --   42.00  65.00  30.48   50
 30  \w     48.00  73.00   0.50    0.85    --   42.00  73.00 143.60   50
 31  \w     54.00  79.00   0.50    0.85    --   46.00  68.00 -87.86   50
 32  \w     54.00  82.00   0.50    0.85    --   46.00  69.00 -18.97   56
 33  \w     52.00  77.00   0.50    0.85    --   46.00  72.00-172.72   50
 34  \w     56.00  81.00   0.50    0.85    --   50.00  72.00 171.36   50
 35  \w     57.00  82.00   0.50    0.85    --   50.00  70.00 -65.00   50
 36  \w    -84.00 -57.00   0.50    0.85    --  -50.00 -70.00  14.18   54
 37  \w    -84.00 -57.00   0.50    0.85    --  -50.00 -71.00  93.74   54
 38  \w     59.00  84.00   0.50    0.85    --   50.00  65.00-120.43   50
 39  \w     57.00  82.00   0.50    0.85    --   50.00  70.00-160.51   50
 40  \w     57.00  82.00   0.50    0.85    --   50.00  71.00-145.64   50
 41  \w     61.00  86.00   0.50    0.85    --   54.00  71.00  14.37   50
 42  \w     61.00  86.00   0.50    0.85    --   54.00  70.00  61.21   50
 43  \w     60.00  85.00   0.50    0.85    --   54.00  72.00 -18.37   50
 44  \w     61.00  86.00   0.50    0.85    --   54.00  70.00 153.92   50
 45  \w     67.00  94.00   0.50    0.85    --   58.00  70.00  78.22   54
 46  \w     64.00  89.00   0.50    0.85    --   58.00  72.00 -80.35   50
 47  \w     65.00  90.00   0.50    0.85    --   58.00  70.00  98.06   50
 48  \w     67.00  92.00   0.50    0.85    --   58.00  64.00-111.53   50
 49  \w     67.00  92.00   0.50    0.85    --   58.00  62.00 137.43   50
 50  \w     65.00  90.00   0.50    0.85    --   58.00  71.00  28.05   50
 51  \w     67.00  92.00   0.50    0.85    --   58.00  62.00 -83.12   50
 52  \w     65.00  90.00   0.50    0.85    --   58.00  71.00  -0.12   50
 53  \w     65.00  90.00   0.50    0.85    --   58.00  71.00 175.41   50
 54  \w     69.00  94.00   0.50    0.85    --   62.00  71.00  67.46   50
 55  \w     69.00  99.00   0.50    0.85    --   62.00  72.00 -59.41   60
 56  \w     70.00  98.00   0.50    0.85    --   62.00  72.00  39.36   56
 57  \w     69.00  94.00   0.50    0.85    --   62.00  70.00 129.90   50
 58  \w     68.00  93.00   0.50    0.85    --   62.00  72.00 148.46   50
 59  \w     69.00  94.00   0.50    0.85    --   62.00  70.00-175.53   50
 60  \w     73.00 100.00   0.50    0.85    --   62.00  63.00-151.00   54
 61  \w     69.00 100.00   0.50    0.85    --   62.00  70.00 -14.41   62
 62  \w     27.00  67.00   0.50    0.85    --   63.37 -95.00 -90.00   80
 63  \w     42.00  72.00   0.50    0.85    --   63.37 -95.00-180.00   60
 64  \w     24.00  63.00   0.50    0.85    --   63.37-125.00 120.00   78
 65  \w     26.00  88.00   0.50    0.85    --   63.37   0.00  30.00  124
 66  \w    -89.00 -30.00   0.50    0.85    --  -63.96 125.00  60.00  118
 67  \w    -78.00 -33.00   0.50    0.85    --  -63.96   0.00 -90.00   90
 68  \w   -100.00 -26.00   0.50    0.85    --  -63.96   0.00 120.00  148
 69  \w    -94.00 -30.00   0.50    0.85    --  -63.96   0.00 -30.00  128
 70  \w    -47.00 -22.00   0.50    0.85    --  -63.96 125.00 -90.00   50
 71  \w    -89.00 -51.00   0.50    0.85    --  -63.96 125.00 -90.00   76
 72  \w    -92.00 -46.00   0.50    0.85    --  -63.96   0.00  30.00   92
 73  \w    -53.00 -27.00   0.50    0.85    --  -63.96 125.00 -30.00   52
 74  \w    -91.00 -55.00   0.50    0.85    --  -63.96 125.00 -30.00   72
 75  \w     71.00  98.00   0.50    0.85    --   66.00  75.00 -81.63   54
 76  \w     73.00  98.00   0.50    0.85    --   66.00  70.00-151.23   50
 77  \w     45.00 107.00   0.50    0.85    --   69.62  19.00 -67.11  124
 78  \w   -100.00 -74.00   0.50    0.85    --  -70.00 -75.00-103.27   52
 79  \w   -105.00 -78.00   0.50    0.85    --  -70.00 -66.00 -63.34   54
 80  \w     75.00 100.00   0.50    0.85    --   70.00  75.00-153.22   50
 81  \w   -106.00 -78.00   0.50    0.85    --  -70.00 -66.00 143.34   56
 82  \w   -109.00 -78.00   0.50    0.85    --  -70.00 -66.00 131.62   62
 83  \w   -102.00 -75.00   0.50    0.85    --  -70.00 -74.00   3.45   54
 84  \w   -101.00 -75.00   0.50    0.85    --  -70.00 -73.00 -41.44   52
 85  \w     75.00 105.00   0.50    0.85    --   70.00  74.00  46.97   60
 86  \w   -110.00 -79.00   0.50    0.85    --  -70.00 -61.00  84.79   62
 87  \w   -101.00 -74.00   0.50    0.85    --  -70.00 -75.00  15.71   54
 88  \w   -105.00 -78.00   0.50    0.85    --  -70.00 -65.00  24.27   54
 89  \w   -103.00 -76.00   0.50    0.85    --  -70.00 -74.00 -29.44   54
 90  \w   -102.00 -75.00   0.50    0.85    --  -70.00 -73.00-111.96   54
 91  \w    -99.00 -32.00   0.50    0.85    --  -73.72 125.00 -60.00  134
 92  \w    -66.00 -32.00   0.50    0.85    --  -73.72 125.00-180.00   68
 93  \w    -99.00 -71.00   0.50    0.85    --  -73.72 125.00-180.00   56
 94  \w    -58.00 -32.00   0.50    0.85    --  -73.72 125.00 120.00   52
 95  \w    -99.00 -74.00   0.50    0.85    --  -73.72 125.00 120.00   50
 96  \w    -65.00 -36.00   0.50    0.85    --  -73.72 125.00   0.00   58
 97  \w    -99.00 -72.00   0.50    0.85    --  -73.72 125.00   0.00   54
 98  \w   -110.00 -78.00   0.50    0.85    --  -74.00 -75.00 132.04   64
 99  \w   -104.00 -77.00   0.50    0.85    --  -74.00 -77.00  77.85   54
100  \w     78.00 103.00   0.50    0.85    --   75.86-125.00   0.00   50
101  \w     42.00  75.00   0.50    0.85    --   75.86-125.00   0.00   66
102  \w   -112.00 -85.00   0.50    0.85    --  -76.78-125.00   0.00   54
103  \w   -102.00 -35.00   0.50    0.85    --  -76.78 125.00  30.00  134
104  \w   -114.00 -87.00   0.50    0.85    --  -76.78-125.00 -30.00   54
105  \w   -117.00 -92.00   0.50    0.85    --  -76.78-125.00 150.00   50
106  \w   -118.00 -90.00   0.50    0.85    --  -76.78-125.00 -90.00   56
107  \w   -113.00 -86.00   0.50    0.85    --  -76.78-125.00  30.00   54
108  \w   -116.00 -79.00   0.50    0.85    --  -76.78-125.00 -60.00   74
109  \w   -115.00 -90.00   0.50    0.85    --  -76.78-125.00-180.00   50
110  \w   -118.00 -85.00   0.50    0.85    --  -76.78-125.00  60.00   66
111  \w   -118.00 -93.00   0.50    0.85    --  -76.78-125.00-120.00   50
112  \w   -110.00 -82.00   0.50    0.85    --  -76.78-125.00 120.00   56
113  \w   -114.00 -87.00   0.50    0.85    --  -76.78-125.00-150.00   54
114  \w   -112.00 -85.00   0.50    0.85    --  -76.78-125.00  90.00   54
115  \w   -111.00 -82.00   0.50    0.85    --  -78.25 -78.00 176.67   58
116  \w    -69.00 -41.00   0.50    0.85    --  -78.25 137.00 -81.91   56
117  \w   -113.00 -87.00   0.50    0.85    --  -78.25 137.00 -81.91   52
118  \w    -90.00 -47.00   0.50    0.85    --  -78.25 143.00 111.12   86
119  \w   -112.00 -38.00   0.50    0.85    --  -78.25 135.00-163.35  148
120  \w   -111.00 -36.00   0.50    0.85    --  -78.25 135.00  54.32  150
121  \w   -111.00 -86.00   0.50    0.85    --  -78.25 -66.00-174.53   50
122  \w   -115.00 -37.00   0.50    0.85    --  -78.25 139.00  82.30  156
123  \w   -112.00 -41.00   0.50    0.85    --  -78.25 138.00-129.10  142
124  \w   -113.00 -82.00   0.50    0.85    --  -78.25 -76.00-123.61   62
125  \w   -114.00 -87.00   0.50    0.85    --  -78.25 -69.00 112.51   54
126  \w   -110.00 -82.00   0.50    0.85    --  -78.25 -78.00   1.84   56
127  \w   -115.00 -54.00   0.50    0.85    --  -78.25 140.00 -33.18  122
128  \w   -113.00 -80.00   0.50    0.85    --  -78.25 -79.00 -62.88   66
129  \w   -113.00 -40.00   0.50    0.85    --  -78.25 136.00 151.04  146
;
_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      0.0924271000
_diffrn_orient_matrix_UB_12      0.0130204000
_diffrn_orient_matrix_UB_13      -0.0633705000
_diffrn_orient_matrix_UB_21      -0.1049632000
_diffrn_orient_matrix_UB_22      0.0484401000
_diffrn_orient_matrix_UB_23      -0.0575329000
_diffrn_orient_matrix_UB_31      0.0541610000
_diffrn_orient_matrix_UB_32      0.1052056000
_diffrn_orient_matrix_UB_33      0.0454093000
_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  0.0506
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.9971
_diffrn_reflns_Laue_measured_fraction_max 0.9698
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            76298
_diffrn_reflns_point_group_measured_fraction_full 0.9971
_diffrn_reflns_point_group_measured_fraction_max 0.9698
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         74.15
_diffrn_reflns_theta_min         2.78
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.664
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.804
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             933.933
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.1625
_refine_diff_density_min         -0.4341
_refine_diff_density_rms         0.0619
_refine_ls_d_res_high            0.8014
_refine_ls_d_res_low             15.9000
_refine_ls_goodness_of_fit_ref   1.0473
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    84
_refine_ls_number_parameters     532
_refine_ls_number_reflns         8744
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0473
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          -0.0009
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0454P)^2^+1.8567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0968
_refine_ls_wR_factor_ref         0.0997
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -12
_reflns_limit_k_max              16
_reflns_limit_k_min              -16
_reflns_limit_l_max              20
_reflns_limit_l_min              0
_reflns_number_gt                7841
_reflns_number_total             8744
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           JW141
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135034
_chemical_oxdiff_formula         'C H N P O S F'
_cell_oxdiff_angle_alpha         94.9446(6)
_cell_oxdiff_angle_beta          99.9551(6)
_cell_oxdiff_angle_gamma         94.9969(7)
_cell_oxdiff_length_a            10.48574(8)
_cell_oxdiff_length_b            13.33953(11)
_cell_oxdiff_length_c            16.22966(12)
_cell_oxdiff_measurement_reflns_used 36308
_cell_oxdiff_volume              2215.55(3)
_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:
 C27(H27), C30(H30), C10(H10), C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C44(H44), C19(H19), C5(H5), C16(H16), C3(H3), C18(H18), C42(H42),
 C40(H40), C43(H43), C25(H25), C41(H41), C23(H23), C4(H4), C34(H34), C24(H24),
 C38(H38), C35(H35), C37(H37), C36(H36)
2.c Idealised Me refined as rotating group:
 C8(H8a,H8b,H8c), C28(H28a,H28b,H28c), C29(H29a,H29b,H29c), C9(H9a,H9b,H9c),
 C20(H20a,H20b,H20c), C11(H11a,H11b,H11c), C31(H31a,H31b,H31c), C12(H12a,H12b,
 H12c), C32(H32a,H32b,H32c)
;
_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 2.114
_oxdiff_exptl_absorpt_empirical_full_min 0.699