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_1560231
_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_sum            'C86 H100 Au B F2 O P2'
_chemical_formula_weight         1457.37
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_hw24
_audit_creation_date             2019-10-15
_audit_creation_method
;
encif (version 1.108)

encifer (version_id = 257312.64)

Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-08 deposited with the CCDC.	2021-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.5291(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.28458(15)
_cell_length_b                   13.79053(15)
_cell_length_c                   47.7699(4)
_cell_measurement_reflns_used    55757
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      25.6110
_cell_measurement_theta_min      2.4620
_cell_volume                     7433.65(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_publication_material
'encif (Wadepohl, 2009-19); encifer 1.7.x (CCDC, 2019)'
_computing_structure_refinement  'ShelXL (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 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -40.00  61.00   0.50   20.00    --   30.55 -77.00 -30.00  202
  2  \w    -38.00  52.00   0.50   20.00    --   30.55 -57.00 150.00  180
  3  \w      5.00 103.00   0.50   20.00    --   30.55  38.00-120.00  196
  4  \w    -15.00  72.00   0.50   20.00    --   30.55 -99.00  90.00  174
  5  \w    -15.00  72.00   0.50   20.00    --   30.55 -99.00 -90.00  174
  6  \w      4.00  99.00   0.50   20.00    --   30.55  71.00-171.69  190
  7  \w      3.00 100.00   0.50   20.00    --   30.55  73.00  94.58  194
  8  \w      5.00 103.00   0.50   20.00    --   30.55  38.00  60.00  196
  9  \w      3.00 100.00   0.50   20.00    --   30.55  73.00 -77.33  194
 10  \w    -42.00   7.00   0.50   20.00    --  -23.50 -77.00 -30.00   98
 11  \w     -6.00  21.00   0.50   20.00    --   26.00  80.00 -57.20   54
 12  \w     -7.00  21.00   0.50   20.00    --   26.00  82.00  96.02   56
 13  \w      2.00 100.00   0.50   20.00    --   30.55  74.00  -1.62  196
 14  \w    -15.00  72.00   0.50   20.00    --   30.55 -99.00 150.00  174
 15  \w     10.00  99.00   0.50   20.00    --   30.55  57.00 -90.00  178
 16  \w    -38.00  52.00   0.50   20.00    --   30.55 -57.00 -30.00  180
 17  \w    -42.00  56.00   0.50   20.00    --   30.55 -38.00  30.00  196
 18  \w    -45.00  45.00   0.50   20.00    --  -23.50  57.00-180.00  180
 19  \w    -42.00   7.00   0.50   20.00    --  -23.50 -77.00  90.00   98
 20  \w      2.00 100.00   0.50   20.00    --   30.55  74.00 132.18  196
 21  \w    -15.00  72.00   0.50   20.00    --   30.55 -99.00-150.00  174
 22  \w      2.00 100.00   0.50   20.00    --   30.55  74.00  47.67  196
 23  \f      0.00  25.00   0.50   20.00 -17.67  30.55 -40.00    --    50
 24  \w    -38.00  52.00   0.50   20.00    --   30.55 -57.00-120.00  180
;
_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      0.0576831861
_diffrn_orient_matrix_UB_12      -0.0155618042
_diffrn_orient_matrix_UB_13      -0.0036932692
_diffrn_orient_matrix_UB_21      -0.0249186775
_diffrn_orient_matrix_UB_22      -0.0380575908
_diffrn_orient_matrix_UB_23      -0.0081244554
_diffrn_orient_matrix_UB_31      -0.0015996206
_diffrn_orient_matrix_UB_32      0.0309113579
_diffrn_orient_matrix_UB_33      -0.0118662480
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.1594
_diffrn_reflns_av_unetI/netI     0.0766
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       73
_diffrn_reflns_limit_l_min       -73
_diffrn_reflns_number            399120
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.204
_diffrn_reflns_theta_min         2.256
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.072
_exptl_absorpt_correction_T_max  0.993
_exptl_absorpt_correction_T_min  0.884
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             3024
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.055
_refine_diff_density_max         1.117
_refine_diff_density_min         -1.322
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     811
_refine_ls_number_reflns         28406
_refine_ls_number_restraints     678
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.1206
_refine_ls_R_factor_gt           0.0764
_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^)+(0.0220P)^2^+28.0226P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1264
_refine_ls_wR_factor_ref         0.1384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18607
_reflns_number_total             28406
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06128j2.cif
_cod_data_source_block           ba_hw24_sq
_cod_depositor_comments
'Adding full bibliography for 1560218--1560233.cif.'
_cod_original_cell_volume        7433.66(14)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1560231
_audit_block_refno               3434
_audit_block_usercomment         FB26_FULL
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.820
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.50
_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. Shared sites
{C27A, C27B}
{C28A, C28B}
{C37A, C37B}
{C38A, C38B}
3. Restrained planarity
 C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34B, C35A, C36A, C37A, C38A
 with sigma of 0.1
 C27B, C28B, C29B, C30B, C31B, C32B, C33B, C38B
 with sigma of 0.1
4. Rigid bond restraints
 C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34B, C35A, C36A, C37A, C38A, C39A,
 C40A, C41A, C42A, C43A, C44A, C45A, C46A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27B, C28B, C29B, C30B, C31B, C32B, C33B, C38B, C37B, C36B, C35B, C34A, C39B,
 C40B, C41B, C42B, C43B, C44B, C45B, C46B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27B \\sim C28B \\sim C29B \\sim C30B \\sim C31B \\sim C32B
\\sim C33B \\sim C38B \\sim C37B \\sim C36B \\sim C35B \\sim C34A \\sim C39B
\\sim C40B \\sim C41B \\sim C42B \\sim C43B \\sim C44B \\sim C45B \\sim C46B
\\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C51 \\sim C52
\\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60
\\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68
\\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C27A \\sim
C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim C34B \\sim
C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim
C42A \\sim C43A \\sim C44A \\sim C45A \\sim C46A: within 1A with sigma of 0.01
and sigma for terminal atoms of 0.01
Uanis(C27A) = Uanis(C27B)
Uanis(C28A) = Uanis(C28B)
Uanis(C29A) = Uanis(C29B)
Uanis(C30A) = Uanis(C30B)
Uanis(C31A) = Uanis(C31B)
Uanis(C32A) = Uanis(C32B)
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(C35A) = Uanis(C35B)
Uanis(C36A) = Uanis(C36B)
Uanis(C37A) = Uanis(C37B)
Uanis(C38A) = Uanis(C38B)
Uanis(C43A) = Uanis(C43B)
Uanis(C44A) = Uanis(C44B)
Uanis(C45A) = Uanis(C45B)
Uanis(C46A) = Uanis(C46B)
6. Rigid body (RIGU) restrains
 Au, C27B, C28B, C29B, C30B, C31B, C32B, C33B, C38B, C37B, C36B, C35B, C34A,
 C39B, C40B, C41B, C42B, C43B, C44B, C45B, C46B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Au, C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34B, C35A, C36A, C37A, C38A,
 C39A, C40A, C41A, C42A, C43A, C44A, C45A, C46A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{C39B, C41B, C42B, C40B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C39B, C40B, C41B, C42B}
{C43B, C45B, C46B, C44B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C43B, C44B, C45B, C46B}
{C27B, C28B, C29B, C30B, C31B, C32B, C33B, C38B, C37B, C36B, C35B, C34A, C39B,
C40B, C41B, C42B, C43B, C44B, C45B, C46B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34B, C35A, C36A, C37A, C38A, C39A,
C40A, C41A, C42A, C43A, C44A, C45A, C46A}
8. Others
 Sof(C27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(C30B)=Sof(H30B)=Sof(C31B)=
 Sof(H31B)=Sof(C32B)=Sof(C33B)=Sof(C38B)=Sof(C37B)=Sof(H37B)=Sof(C36B)=
 Sof(C35B)=Sof(H35B)=Sof(C34A)=Sof(H34A)=Sof(C39B)=Sof(C40B)=Sof(H40A)=
 Sof(H40B)=Sof(H40C)=Sof(C41B)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42B)=
 Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43B)=Sof(C44B)=Sof(H44A)=Sof(H44B)=
 Sof(H44C)=Sof(C45B)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46B)=Sof(H46A)=
 Sof(H46B)=Sof(H46C)=1-FVAR(1)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(C33A)=Sof(C34B)=Sof(H34B)=Sof(C35A)=Sof(H35A)=
 Sof(C36A)=Sof(C37A)=Sof(H37A)=Sof(H37C)=Sof(C38A)=Sof(C39A)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=Sof(C44A)=Sof(H44D)=
 Sof(H44E)=Sof(H44F)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46A)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=FVAR(1)
9.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21), C24(H24)
9.b Secondary CH2 refined with riding coordinates:
 C37A(H37A,H37C)
9.c Me refined with riding coordinates:
 C40B(H40A,H40B,H40C), C41B(H41A,H41B,H41C), C42B(H42A,H42B,H42C), C44B(H44A,
 H44B,H44C), C45B(H45A,H45B,H45C), C46B(H46A,H46B,H46C), C40A(H40D,H40E,H40F),
 C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F), C44A(H44D,H44E,H44F), C45A(H45D,
 H45E,H45F), C46A(H46D,H46E,H46F)
9.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13),
 C28B(H28B), C30B(H30B), C31B(H31B), C37B(H37B), C35B(H35B), C34A(H34A),
 C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
 C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C70(H70), C71(H71), C72(H72),
  C73(H73), C74(H74), C28A(H28A), C30A(H30A), C31A(H31A), C34B(H34B), C35A(H35A)
9.e 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)
;
_shelx_hkl_checksum              72717
_shelx_fab_checksum              60618
_platon_squeeze_void_probe_radius 1.20
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.147
_oxdiff_exptl_absorpt_empirical_full_min 0.877
_shelx_res_checksum              37064
_cell_oxdiff_length_a            11.28502(15)
_cell_oxdiff_length_b            13.78891(13)
_cell_oxdiff_length_c            47.7736(3)
_cell_oxdiff_angle_alpha         89.9900(6)
_cell_oxdiff_angle_beta          90.5153(8)
_cell_oxdiff_angle_gamma         90.0221(9)
_cell_oxdiff_volume              7433.66(13)
_cell_oxdiff_measurement_reflns_used 55758