A 2,2′-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C‒P bond formation
Wagner, Hannah K.; Wadepohl, Hubert; Ballmann, Joachim; Chemical Science 12 (2021) 3693–3701; doi:10.1039/D0SC06128J

data_1560232
_publ_section_title
;
 A 2,2&#x2032;-diphosphinotolane as a versatile precursor for the
 synthesis of P-ylidic mesoionic carbenes via reversible C--P bond
 formation
;
_journal_issue                   10
_journal_name_full               'Chemical Science'
_journal_page_first              3693
_journal_page_last               3701
_journal_paper_doi               10.1039/D0SC06128J
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C29 H36 Mo O3 P2'
_chemical_formula_sum            'C29 H36 Mo O3 P2'
_chemical_formula_weight         590.46
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_hw37
_audit_creation_date             2020-06-23
_audit_creation_method
;
encif (version 1.113)

encifer (version_id = 274361.64)

Olex2 1.3
(compiled 2020.01.31 svn.r88ba2a3 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-10-08 deposited with the CCDC.	2021-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.65317(6)
_cell_length_b                   16.11165(8)
_cell_length_c                   22.26048(9)
_cell_measurement_reflns_used    105552
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      71.0890
_cell_measurement_theta_min      4.3900
_cell_volume                     5614.06(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_publication_material
'encif (Wadepohl, 2009-19); encifer (Allen et al., 2004)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SIR2019 (Giacovazzo et al., 2019)'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -68.00 -11.00   1.00    2.00    --    0.00 142.00  31.00   57
  2  \w    -59.00  -4.00   1.00    2.00    --    0.00 128.00-139.00   55
  3  \w     33.00 122.00   1.00    5.00    --   54.00-142.00 -24.00   89
  4  \w     26.00 113.00   1.00    5.00    --   54.00-128.00 146.00   87
  5  \w     37.00 120.00   1.00   15.00    --  108.00-128.00 146.00   83
  6  \w     38.00 130.00   1.00   15.00    --  108.00-142.00 -24.00   92
  7  \w     84.00 177.00   1.00   15.00    --  108.00 142.00  31.00   93
  8  \w     93.00 178.00   1.00   15.00    --  108.00 128.00-139.00   85
  9  \w    -21.00  69.00   1.00    2.00    --    0.00  57.00 150.00   90
 10  \w    -70.00  30.00   1.00    2.00    --    0.00 -77.00  30.00  100
 11  \w    -30.00  70.00   1.00    2.00    --    0.00  77.00 -30.00  100
 12  \w    -37.00  -3.00   1.00    2.00    --   22.00 127.00-103.48   34
 13  \w    -25.00   1.00   1.00    5.00    --   30.00 121.00  13.59   26
 14  \w     -9.00  18.00   1.00    5.00    --   34.00 102.00 130.64   27
 15  \w     -2.00  24.00   1.00    5.00    --   38.00  96.00 -98.44   26
 16  \w      8.00  38.00   1.00    5.00    --   42.00  84.00 -95.87   30
 17  \w      6.00  33.00   1.00    5.00    --   42.00  88.00 -37.54   27
 18  \w      5.00  32.00   1.00    5.00    --   42.00  90.00  83.98   27
 19  \w     13.00  40.00   1.00    5.00    --   46.00  83.00  10.01   27
 20  \w     13.00  40.00   1.00    5.00    --   46.00  83.00-134.22   27
 21  \w     13.00  40.00   1.00    5.00    --   46.00  83.00  38.53   27
 22  \w     17.00  45.00   1.00    5.00    --   50.00  82.00 124.59   28
 23  \w     17.00  45.00   1.00    5.00    --   50.00  82.00 -26.98   28
 24  \w     17.00  45.00   1.00    5.00    --   50.00  82.00-172.41   28
 25  \w     18.00  45.00   1.00    5.00    --   50.00  81.00  42.12   27
 26  \w     17.00  45.00   1.00    5.00    --   50.00  82.00 -61.18   28
 27  \w     17.00  45.00   1.00    5.00    --   50.00  82.00 152.46   28
 28  \w     17.00  45.00   1.00    5.00    --   50.00  82.00  71.71   28
 29  \w     18.00  45.00   1.00    5.00    --   50.00  81.00 -75.73   27
 30  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 -14.73  100
 31  \w     24.00 124.00   1.00    5.00    --   54.00  77.00  60.00  100
 32  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 -90.00  100
 33  \w    -15.00  75.00   1.00    5.00    --   54.00 -57.00 150.00   90
 34  \w     24.00 124.00   1.00    5.00    --   54.00  77.00-120.00  100
 35  \w    -18.00  80.00   1.00    5.00    --   54.00 -38.00 -60.00   98
 36  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 -30.00  100
 37  \w      1.00  96.00   1.00    5.00    --   54.00 -99.00 -60.00   95
 38  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 150.00  100
 39  \w     28.00 128.00   1.00    5.00    --   58.00  77.00  66.65  100
 40  \w     29.00 128.00   1.00    5.00    --   58.00  76.00  85.78   99
 41  \w     28.00 128.00   1.00    5.00    --   58.00  77.00   9.34  100
 42  \w     28.00 128.00   1.00    5.00    --   58.00  77.00  95.85  100
 43  \w     30.00 127.00   1.00    5.00    --   58.00  73.00-166.30   97
 44  \w     28.00 128.00   1.00    5.00    --   58.00  77.00-152.37  100
 45  \w     28.00 128.00   1.00    5.00    --   58.00  77.00 149.33  100
 46  \w     29.00 128.00   1.00    5.00    --   58.00  75.00  49.89   99
 47  \w     28.00 128.00   1.00    5.00    --   58.00  77.00 167.90  100
 48  \w     28.00 128.00   1.00    5.00    --   58.00  77.00 -10.06  100
 49  \w     34.00 132.00   1.00    5.00    --   62.00  74.00  68.39   98
 50  \w     34.00 132.00   1.00    5.00    --   62.00  74.00 -86.44   98
 51  \w     34.00 131.00   1.00    5.00    --   62.00  73.00  99.49   97
 52  \w     33.00 132.00   1.00    5.00    --   62.00  75.00 111.56   99
 53  \w     33.00 132.00   1.00    5.00    --   62.00  75.00 132.79   99
 54  \w     32.00 132.00   1.00    5.00    --   62.00  77.00-150.29  100
 55  \w     34.00 132.00   1.00    5.00    --   62.00  74.00-110.33   98
 56  \w     34.00 129.00   1.00    5.00    --   62.00  74.00   8.91   95
 57  \w     34.00  60.00   1.00    5.00    --   62.00  75.00 101.68   26
 58  \w     35.00  68.00   1.00    5.00    --   62.00  77.00 -73.81   33
 59  \w     40.00  65.00   1.00    5.00    --   62.00  64.00-159.65   25
 60  \w     32.00  58.00   1.00    5.00    --   62.00  77.00 -34.51   26
 61  \w     37.00  63.00   1.00    5.00    --   66.00  75.00 159.18   26
 62  \w     41.00  67.00   1.00    5.00    --   66.00  77.00  62.83   26
 63  \w     37.00  63.00   1.00    5.00    --   66.00  77.00 -32.37   26
 64  \w     39.00  79.00   1.00    5.00    --   66.00  71.00 107.32   40
 65  \w     36.00  62.00   1.00    5.00    --   66.00  77.00-111.22   26
 66  \w     37.00  63.00   1.00    5.00    --   66.00  77.00  16.08   26
 67  \w     43.00  69.00   1.00    5.00    --   70.00  71.00  56.34   26
 68  \w     40.00  82.00   1.00    5.00    --   70.00  77.00 107.46   42
 69  \w     44.00  70.00   1.00    5.00    --   70.00  71.00-135.16   26
 70  \w     42.00  76.00   1.00    5.00    --   70.00  76.00 -27.34   34
 71  \w     49.00  75.00   1.00    5.00    --   70.00  75.00  73.53   26
 72  \w     41.00  75.00   1.00    5.00    --   70.00  77.00 -62.23   34
 73  \w    112.00 138.00   1.00    5.00    --   70.00  72.00-151.77   26
 74  \w     43.00  69.00   1.00    5.00    --   70.00  72.00-151.77   26
 75  \w     52.00  78.00   1.00    5.00    --   74.00  69.00   4.90   26
 76  \w     45.00 121.00   1.00    5.00    --   74.00  75.00-103.80   76
 77  \w     46.00  72.00   1.00    5.00    --   74.00  73.00-172.12   26
 78  \w     46.00  72.00   1.00    5.00    --   74.00  75.00  11.65   26
 79  \w     47.00  75.00   1.00    5.00    --   74.00  76.00 -19.49   28
 80  \w    107.00 134.00   1.00    5.00    --   74.00  77.00  22.74   27
 81  \w     44.00  72.00   1.00    5.00    --   74.00  77.00  22.74   28
 82  \w     44.00  70.00   1.00    5.00    --   74.00  77.00 -78.91   26
 83  \w     49.00  88.00   1.00    5.00    --   74.00  71.00 145.29   39
 84  \w     46.00  79.00   1.00    5.00    --   74.00  75.00 -86.03   33
 85  \w     44.00  70.00   1.00    5.00    --   74.00  77.00  89.24   26
 86  \w     52.00  78.00   1.00    5.00    --   74.00  68.00-134.38   26
 87  \w     46.00  76.00   1.00    5.00    --   74.00  73.00 125.76   30
 88  \w     50.00  76.00   1.00    5.00    --   78.00  74.00  58.38   26
 89  \w     50.00  76.00   1.00    5.00    --   78.00  73.00-135.64   26
 90  \w     50.00  86.00   1.00    5.00    --   78.00  73.00 -74.48   36
 91  \w     54.00  90.00   1.00    5.00    --   78.00  70.00 -23.25   36
 92  \w     56.00 132.00   1.00    5.00    --   78.00  62.00  60.72   76
 93  \w     50.00 141.00   1.00    5.00    --   78.00  74.00 -99.28   91
 94  \w     66.00  92.00   1.00    5.00    --   78.00  55.00  43.37   26
 95  \w     56.00  82.00   1.00    5.00    --   78.00  64.00 -50.17   26
 96  \w     48.00  75.00   1.00    5.00    --   78.00  77.00 170.57   27
 97  \w     49.00  75.00   1.00    5.00    --   78.00  76.00 117.04   26
 98  \w     62.00  87.00   1.00    5.00    --   78.00  67.00-168.89   25
 99  \w     59.00  99.00   1.00   15.00    --   82.00  65.00 -50.20   40
100  \w     62.00  88.00   1.00   15.00    --   82.00  60.00 -10.45   26
101  \w     59.00  85.00   1.00   15.00    --   82.00  72.00-140.17   26
102  \w     52.00  80.00   1.00   15.00    --   82.00  77.00 134.86   28
103  \w     54.00  80.00   1.00   15.00    --   82.00  77.00  79.37   26
104  \w     59.00  85.00   1.00   15.00    --   82.00  66.00   1.65   26
105  \w     58.00 126.00   1.00   15.00    --   82.00  71.00-117.63   68
106  \w     62.00  94.00   1.00   15.00    --   82.00  62.00 -63.94   32
107  \w     59.00  85.00   1.00   15.00    --   86.00  72.00-164.57   26
108  \w     58.00  84.00   1.00   15.00    --   86.00  74.00  -5.31   26
109  \w     65.00 101.00   1.00   15.00    --   86.00  54.00  52.59   36
110  \w     67.00 116.00   1.00   15.00    --   86.00  66.00 104.38   49
111  \w     64.00  90.00   1.00   15.00    --   86.00  64.00-142.72   26
112  \w     77.00 103.00   1.00   15.00    --   90.00  62.00 134.49   26
113  \w     70.00  98.00   1.00   15.00    --   90.00  52.00  89.44   28
114  \w     69.00 140.00   1.00   15.00    --   94.00  69.00 -92.83   71
115  \w     69.00 104.00   1.00   15.00    --   94.00  69.00  -5.34   35
116  \w     66.00  93.00   1.00   15.00    --   94.00  75.00  26.38   27
117  \w     74.00 106.00   1.00   15.00    --   98.00  67.00  26.88   32
118  \w     68.00  94.00   1.00   15.00    --   98.00  77.00 103.53   26
119  \w     69.00 146.00   1.00   15.00    --   98.00  76.00-129.80   77
120  \w     76.00 108.00   1.00   15.00    --  102.00  72.00  -2.77   32
121  \w     82.00 160.00   1.00   15.00    --  108.00  38.00-180.00   78
122  \w     78.00 104.00   1.00   15.00    --  108.00  77.00 -60.00   26
123  \w     88.00 121.00   1.00   15.00    --  108.00  62.00 176.70   33
124  \w     85.00 111.00   1.00   15.00    --  108.00  64.00  60.00   26
125  \w     86.00 113.00   1.00   15.00    --  108.00  64.00-120.00   27
126  \w     36.00  93.00   1.00   15.00    --  108.00 -92.00-180.00   57
127  \w     78.00 104.00   1.00   15.00    --  108.00  77.00  60.00   26
128  \w     87.00 175.00   1.00   15.00    --  108.00  64.00  30.00   88
129  \w     78.00 104.00   1.00   15.00    --  108.00  77.00  30.00   26
130  \w     87.00 116.00   1.00   15.00    --  108.00  64.00 -30.00   29
131  \w     46.00  74.00   1.00   15.00    --  108.00 -92.00  60.00   28
132  \w     78.00 105.00   1.00   15.00    --  108.00  77.00 120.00   27
133  \w     81.00 106.00   1.00   15.00    --  108.00  74.00 103.14   25
134  \w     36.00  84.00   1.00   15.00    --  108.00 -92.00-120.00   48
135  \w     86.00 174.00   1.00   15.00    --  108.00  64.00 -90.00   88
136  \w     37.00  83.00   1.00   15.00    --  108.00 -92.00 150.00   46
137  \w     86.00 175.00   1.00   15.00    --  108.00  64.00-180.00   89
138  \w     79.00 105.00   1.00   15.00    --  108.00 -92.00 -90.00   26
139  \w     78.00 104.00   1.00   15.00    --  108.00  77.00 -90.00   26
140  \w     85.00 129.00   1.00   15.00    --  108.00  64.00-150.74   44
141  \w     78.00 104.00   1.00   15.00    --  108.00  77.00-180.00   26
142  \w     85.00 111.00   1.00   15.00    --  108.00  64.00 150.00   26
143  \w    139.00 165.00   1.00   15.00    --  108.00  64.00 -60.00   26
144  \w     86.00 111.00   1.00   15.00    --  108.00  64.00 -60.00   25
145  \w     80.00 177.00   1.00   15.00    --  108.00  77.00 -30.00   97
146  \w    119.00 178.00   1.00   15.00    --  108.00  77.00-150.00   59
147  \w    138.00 164.00   1.00   15.00    --  108.00  77.00 150.00   26
148  \w     84.00 150.00   1.00   15.00    --  108.00  38.00 120.00   66
149  \w     85.00 152.00   1.00   15.00    --  108.00  38.00  90.00   67
150  \w     85.00 111.00   1.00   15.00    --  108.00  38.00   0.00   26
151  \w     78.00 104.00   1.00   15.00    --  108.00  77.00 150.00   26
152  \w     78.00 104.00   1.00   15.00    --  108.00  77.00-150.00   26
153  \w     84.00 160.00   1.00   15.00    --  108.00  38.00 -30.00   76
154  \w     78.00 156.00   1.00   15.00    --  108.00  77.00   0.00   78
155  \w     48.00 108.00   1.00   15.00    --  108.00 -92.00   0.00   60
156  \w     90.00 175.00   1.00   15.00    --  108.00  64.00 120.00   85
157  \w     79.00 105.00   1.00   15.00    --  108.00  77.00-120.00   26
158  \w     85.00 173.00   1.00   15.00    --  108.00  64.00  90.00   88
159  \w     41.00 130.00   1.00   15.00    --  108.00 -64.00 -90.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0074111000
_diffrn_orient_matrix_UB_12      0.0034149000
_diffrn_orient_matrix_UB_13      0.0689883000
_diffrn_orient_matrix_UB_21      -0.0948721000
_diffrn_orient_matrix_UB_22      0.0247244000
_diffrn_orient_matrix_UB_23      0.0043806000
_diffrn_orient_matrix_UB_31      -0.0251636000
_diffrn_orient_matrix_UB_32      -0.0922573000
_diffrn_orient_matrix_UB_33      0.0037444000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0085
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            201982
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.147
_diffrn_reflns_theta_min         3.972
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.116
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.636
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
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    1.397
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2448
_exptl_crystal_size_max          0.121
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         5421
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0201
_refine_ls_R_factor_gt           0.0192
_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^)+(0.0175P)^2^+4.0723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0447
_refine_ls_wR_factor_ref         0.0451
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5263
_reflns_number_total             5421
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06128j2.cif
_cod_data_source_block           ba_hw37
_cod_depositor_comments
'Adding full bibliography for 1560218--1560233.cif.'
_cod_database_code               1560232
_audit_block_refno               3582
_audit_block_usercomment         'HW316, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.629
_shelx_estimated_absorpt_t_min   0.629
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2018/3
_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:
 C15(H15), C18(H18), C21(H21), C24(H24)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.536
_oxdiff_exptl_absorpt_empirical_full_min 0.910
_shelx_res_checksum              55997
_cell_oxdiff_length_a            15.65103(14)
_cell_oxdiff_length_b            16.11907(18)
_cell_oxdiff_length_c            22.25328(18)
_cell_oxdiff_angle_alpha         89.9865(8)
_cell_oxdiff_angle_beta          90.0123(7)
_cell_oxdiff_angle_gamma         90.0072(8)
_cell_oxdiff_volume              5614.06(9)
_cell_oxdiff_measurement_reflns_used 105552