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_1560230
_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, 1.5(C4 H8 O)'
_chemical_formula_sum            'C35 H48 Mo O4.5 P2'
_chemical_formula_weight         698.61
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                en_hw32
_audit_creation_date             2020-04-22
_audit_creation_method
;
encif (version 1.112)

encifer (version_id = 270009.64)

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                 113.9169(13)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   32.5140(4)
_cell_length_b                   11.57882(9)
_cell_length_c                   39.5477(4)
_cell_measurement_reflns_used    78855
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.9420
_cell_measurement_theta_min      2.9580
_cell_volume                     13610.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.77a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.77a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.77a (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    'SUPERFLIP (Palatinus, 2007-2009)'
_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 0.990
_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    -70.00  30.00   1.00    1.50    --    0.00 -77.00-120.00  100
  2  \w    -30.00  70.00   1.00    1.50    --    0.00  77.00   0.00  100
  3  \w    -21.00  69.00   1.00    1.50    --    0.00  57.00-150.00   90
  4  \w    -40.00   3.00   1.00    1.50    --   14.00 119.00-105.07   43
  5  \w     -2.00  24.00   1.00    3.00    --   38.00  96.00   3.91   26
  6  \w     -1.00  27.00   1.00    3.00    --   38.00  93.00-156.94   28
  7  \w     18.00  45.00   1.00    3.00    --   50.00  81.00 -88.40   27
  8  \w     18.00  45.00   1.00    3.00    --   50.00  81.00-172.32   27
  9  \w     17.00  45.00   1.00    3.00    --   50.00  82.00  47.90   28
 10  \w     17.00  45.00   1.00    3.00    --   50.00  82.00  90.17   28
 11  \w     17.00  45.00   1.00    3.00    --   50.00  82.00 117.67   28
 12  \w     18.00  45.00   1.00    3.00    --   50.00  80.00 -23.42   27
 13  \w     24.00 124.00   1.00    3.00    --   54.00  77.00-120.00  100
 14  \w      1.00  96.00   1.00    3.00    --   54.00 -99.00  30.00   95
 15  \w     24.00 124.00   1.00    3.00    --   54.00  77.00 -60.00  100
 16  \w      1.00  96.00   1.00    3.00    --   54.00 -99.00-180.00   95
 17  \w     24.00 124.00   1.00    3.00    --   54.00  77.00  30.00  100
 18  \w    -15.00  75.00   1.00    3.00    --   54.00 -57.00-120.00   90
 19  \w     25.00 124.00   1.00    3.00    --   54.00  76.00 -19.20   99
 20  \w     28.00 128.00   1.00    3.00    --   58.00  77.00 -63.98  100
 21  \w     29.00 128.00   1.00    3.00    --   58.00  75.00  12.48   99
 22  \w     29.00 128.00   1.00    3.00    --   58.00  75.00-138.69   99
 23  \w     28.00 128.00   1.00    3.00    --   58.00  77.00 115.11  100
 24  \w     33.00 132.00   1.00    3.00    --   62.00  75.00  54.89   99
 25  \w     33.00 132.00   1.00    3.00    --   62.00  75.00  22.81   99
 26  \w     34.00 131.00   1.00    3.00    --   62.00  73.00 -99.66   97
 27  \w     38.00 136.00   1.00    3.00    --   66.00  74.00  87.58   98
 28  \w     45.00 136.00   1.00    3.00    --   66.00  53.00  -7.28   91
 29  \w     37.00 136.00   1.00    3.00    --   66.00  76.00  75.79   99
 30  \w     38.00 135.00   1.00    3.00    --   66.00  73.00-122.08   97
 31  \w     46.00 138.00   1.00    3.00    --   70.00  67.00  58.87   92
 32  \w     41.00 140.00   1.00    3.00    --   70.00  75.00 137.28   99
 33  \w     42.00 139.00   1.00    3.00    --   70.00  73.00 169.65   97
 34  \w     40.00 140.00   1.00    3.00    --   70.00  77.00-175.15  100
 35  \w     45.00 138.00   1.00    3.00    --   70.00  69.00   6.49   93
 36  \w     51.00 141.00   1.00    3.00    --   74.00  64.00-141.20   90
 37  \w     53.00 144.00   1.00    3.00    --   74.00  53.00  -2.02   91
 38  \w     51.00 142.00   1.00    3.00    --   74.00  66.00  83.20   91
 39  \w     53.00 143.00   1.00    3.00    --   74.00  55.00 -72.35   90
 40  \w     51.00 141.00   1.00    3.00    --   74.00  64.00 -54.74   90
 41  \w     50.00 147.00   1.00    3.00    --   78.00  73.00 145.20   97
 42  \w     54.00 152.00   1.00    6.00    --   82.00  74.00 171.09   98
 43  \w     55.00 151.00   1.00    6.00    --   82.00  72.00 160.73   96
 44  \w     63.00 157.00   1.00    6.00    --   86.00  48.00 135.28   94
 45  \w     61.00 160.00   1.00    6.00    --   90.00  76.00 147.66   99
 46  \w     64.00 159.00   1.00    6.00    --   90.00  70.00  43.80   95
 47  \w     71.00 167.00   1.00    6.00    --   98.00  71.00  23.46   96
 48  \w     76.00 168.00   1.00    6.00    --   98.00  51.00  81.15   92
 49  \w     78.00 178.00   1.00    6.00    --  108.00  77.00 -90.00  100
 50  \w     85.00 175.00   1.00    6.00    --  108.00  64.00  90.00   90
 51  \w     78.00 178.00   1.00    6.00    --  108.00  77.00 150.00  100
 52  \w     36.00 113.00   1.00    6.00    --  108.00-111.00 150.00   77
 53  \w     85.00 175.00   1.00    6.00    --  108.00  64.00   0.00   90
 54  \w     36.00 113.00   1.00    6.00    --  108.00-111.00 -60.00   77
 55  \w     85.00 175.00   1.00    6.00    --  108.00  64.00 -60.00   90
 56  \w     78.00 178.00   1.00    6.00    --  108.00  77.00-150.00  100
 57  \w     85.00 175.00   1.00    6.00    --  108.00  64.00 120.00   90
 58  \w     85.00 175.00   1.00    6.00    --  108.00  64.00 150.00   90
 59  \w     85.00 175.00   1.00    6.00    --  108.00  64.00  60.00   90
 60  \w     85.00 175.00   1.00    6.00    --  108.00  64.00-180.00   90
 61  \w     82.00 178.00   1.00    6.00    --  108.00  38.00 120.00   96
 62  \w     82.00 178.00   1.00    6.00    --  108.00  38.00  30.00   96
 63  \w     85.00 175.00   1.00    6.00    --  108.00  64.00 -30.00   90
 64  \w     85.00 175.00   1.00    6.00    --  108.00  64.00 -90.00   90
 65  \w     82.00 178.00   1.00    6.00    --  108.00  38.00 -90.00   96
 66  \w     85.00 175.00   1.00    6.00    --  108.00  64.00-150.00   90
 67  \w     38.00 138.00   1.00    6.00    --  108.00 -77.00-180.00  100
 68  \w     78.00 178.00   1.00    6.00    --  108.00  77.00  90.00  100
 69  \w     78.00 178.00   1.00    6.00    --  108.00  77.00 120.00  100
 70  \w     38.00 138.00   1.00    6.00    --  108.00 -77.00 -30.00  100
 71  \w     36.00 113.00   1.00    6.00    --  108.00-111.00  60.00   77
 72  \w     82.00 178.00   1.00    6.00    --  108.00  38.00-120.00   96
 73  \w     36.00 113.00   1.00    6.00    --  108.00-111.00-180.00   77
 74  \w     78.00 178.00   1.00    6.00    --  108.00  77.00  60.00  100
 75  \w     36.00 109.00   1.00    6.00    --  108.00 -92.00 -90.00   73
 76  \w     85.00 168.00   1.00    6.00    --  108.00  64.00-120.00   83
 77  \w     80.00 106.00   1.00    6.00    --  108.00  77.00 -60.00   26
 78  \w     80.00 106.00   1.00    6.00    --  108.00  77.00-180.00   26
 79  \w     84.00 141.00   1.00    6.00    --  108.00  38.00 -60.00   57
 80  \w     84.00 146.00   1.00    6.00    --  108.00  38.00   0.00   62
 81  \w    141.00 167.00   1.00    6.00    --  108.00  77.00 -30.00   26
 82  \w     78.00 103.00   1.00    6.00    --  108.00  77.00 -30.00   25
 83  \w     78.00 104.00   1.00    6.00    --  108.00  77.00-120.00   26
 84  \w    116.00 171.00   1.00    6.00    --  108.00  77.00  30.00   55
 85  \w     80.00 112.00   1.00    6.00    --  108.00  77.00  30.00   32
 86  \f     30.00 300.00   1.00    0.20   0.00   0.00   0.00    --   270
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0309034000
_diffrn_orient_matrix_UB_12      0.0848167000
_diffrn_orient_matrix_UB_13      0.0292839000
_diffrn_orient_matrix_UB_21      -0.0042533000
_diffrn_orient_matrix_UB_22      0.0868442000
_diffrn_orient_matrix_UB_23      -0.0307381000
_diffrn_orient_matrix_UB_31      -0.0413951000
_diffrn_orient_matrix_UB_32      0.0544141000
_diffrn_orient_matrix_UB_33      0.0034600000
_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  0.0567
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            223964
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.579
_diffrn_reflns_theta_min         2.444
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.339
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.761
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.77a (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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_description       block
_exptl_crystal_F_000             5856
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.066
_refine_diff_density_max         2.260
_refine_diff_density_min         -1.295
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     782
_refine_ls_number_reflns         13157
_refine_ls_number_restraints     120
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0417
_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^)+(0.0383P)^2^+85.9290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0976
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12071
_reflns_number_total             13157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06128j2.cif
_cod_data_source_block           ba_hw32
_cod_depositor_comments
'Adding full bibliography for 1560218--1560233.cif.'
_cod_original_cell_volume        13610.3(3)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_original_formula_sum        'C35 H48 Mo O4.50 P2'
_cod_database_code               1560230
_audit_block_refno               3532
_audit_block_usercomment         'HW304, block, red'
_shelx_estimated_absorpt_t_max   0.671
_shelx_estimated_absorpt_t_min   0.671
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 O81, C82, C83, C84, C85, O91, C92, C93, C94, C95, O101, C102, C103, C104, C105
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Same fragment restrains
{O81, C82, C83, C84, C85} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O91, C92, C93, C94, C95}
{O81, C82, C83, C84, C85} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O101, C102, C103, C104, C105}
4.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21), C24(H24), C65(H65), C68(H68), C71(H71), C73(H73)
4.b Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C92(H92A,
 H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B), C102(H10A,H10B),
 C103(H10C,H10D), C104(H10E,H10F), C105(H10G,H10H)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C53(H53), C54(H54), C55(H55), C56(H56), C59(H59), C60(H60), C61(H61), C62(H62)
4.d 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), C42(H42A,H42B,H42C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C),
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.539
_oxdiff_exptl_absorpt_empirical_full_min 0.395
_shelx_res_checksum              88646
_cell_oxdiff_length_a            32.4949(5)
_cell_oxdiff_length_b            11.58066(15)
_cell_oxdiff_length_c            39.5422(4)
_cell_oxdiff_angle_alpha         90.0314(10)
_cell_oxdiff_angle_beta          113.8431(12)
_cell_oxdiff_angle_gamma         89.9818(11)
_cell_oxdiff_volume              13610.3(3)
_cell_oxdiff_measurement_reflns_used 78855