Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: Facile access to 1,2,3-triphosphol-2-ides
Ghadwal, Rajendra S.; Rottschäfer, Dennis; Blomeyer, Sebastian; Neumann, Beate; Stammler, Georg; Chemical Science  (2019) –; doi:10.1039/C9SC04441H

data_1552452
_publ_section_title
;
 Direct functionalization of white phosphorus with anionic dicarbenes and
 mesoionic carbenes: Facile access to 1,2,3-triphosphol-2-ides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC04441H
_journal_year                    2019
_chemical_formula_moiety         'C40 H44 N3 O5 P3 W, 1.5(C7 H8)'
_chemical_formula_sum            'C50.5 H56 N3 O5 P3 W'
_chemical_formula_weight         1061.74
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-27
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2019-07-10 deposited with the CCDC.    2019-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                106.1610(10)
_cell_angle_beta                 98.4870(10)
_cell_angle_gamma                100.5390(10)
_cell_formula_units_Z            2
_cell_length_a                   12.0860(2)
_cell_length_b                   13.1486(2)
_cell_length_c                   16.9350(2)
_cell_measurement_reflns_used    58491
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3490
_cell_measurement_theta_min      2.7300
_cell_volume                     2484.48(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -116.00  -5.00   1.00    2.00    --  -38.50 -19.00   0.00  111
  2  \w    -64.00  30.00   1.00    2.00    --  -38.50  57.00   0.00   94
  3  \w    -59.00  33.00   1.00    2.00    --  -38.50  38.00 120.00   92
  4  \w     22.00 114.00   1.00    2.00    --   42.89  38.00 -30.00   92
  5  \w     13.00 114.00   1.00    2.00    --   42.89  77.00  60.00  101
  6  \w     13.00 114.00   1.00    2.00    --   42.89  77.00 120.00  101
  7  \w     22.00 114.00   1.00    2.00    --   42.89  38.00 150.00   92
  8  \w      1.00  82.00   1.00    2.00    --   42.89 -99.00  90.00   81
  9  \w     18.00 111.00   1.00    2.00    --   42.89  57.00-150.00   93
 10  \w     13.00 114.00   1.00    2.00    --   42.89  77.00 -30.00  101
 11  \w     13.00 114.00   1.00    2.00    --   42.89  77.00-150.00  101
 12  \w     13.00 114.00   1.00    2.00    --   42.89  77.00 -90.00  101
 13  \w    -26.00  68.00   1.00    2.00    --   42.89 -57.00-180.00   94
 14  \w     41.00 118.00   1.00    8.00    --  111.00-125.00 -90.00   77
 15  \w     89.00 178.00   1.00    8.00    --  111.00  45.00 -60.00   89
 16  \w     85.00 178.00   1.00    8.00    --  111.00  61.00 -60.00   93
 17  \w     81.00 178.00   1.00    8.00    --  111.00  77.00 150.00   97
 18  \w     83.00 178.00   1.00    8.00    --  111.00  70.00  16.73   95
 19  \w     85.00 178.00   1.00    8.00    --  111.00  61.00-120.00   93
 20  \w     81.00 178.00   1.00    8.00    --  111.00  77.00  30.00   97
 21  \w     81.00 178.00   1.00    8.00    --  111.00  77.00-120.00   97
 22  \w     81.00 178.00   1.00    8.00    --  111.00  77.00  60.00   97
 23  \w     81.00 178.00   1.00    8.00    --  111.00  77.00 -60.00   97
 24  \w     81.00 178.00   1.00    8.00    --  111.00  77.00 -90.00   97
 25  \w     85.00 178.00   1.00    8.00    --  111.00  61.00  90.00   93
 26  \w     85.00 178.00   1.00    8.00    --  111.00  61.00-180.00   93
 27  \w     85.00 178.00   1.00    8.00    --  111.00  61.00 -90.00   93
 28  \w     81.00 178.00   1.00    8.00    --  111.00  77.00   0.00   97
 29  \w     85.00 178.00   1.00    8.00    --  111.00  61.00 120.00   93
 30  \w     94.00 178.00   1.00    8.00    --  111.00 125.00 -60.00   84
 31  \w     81.00 178.00   1.00    8.00    --  111.00  77.00 120.00   97
 32  \w     85.00 178.00   1.00    8.00    --  111.00  61.00-150.00   93
 33  \w     41.00 118.00   1.00    8.00    --  111.00-125.00 -60.00   77
 34  \w     31.00 110.00   1.00    8.00    --  111.00 -94.00  90.00   79
 35  \w     85.00 178.00   1.00    8.00    --  111.00  61.00   0.00   93
 36  \w     81.00 178.00   1.00    8.00    --  111.00  77.00-150.00   97
 37  \w     41.00 118.00   1.00    8.00    --  111.00-125.00  60.00   77
 38  \w     85.00 178.00   1.00    8.00    --  111.00  61.00  60.00   93
 39  \w     94.00 178.00   1.00    8.00    --  111.00 125.00 -30.00   84
 40  \w     89.00 178.00   1.00    8.00    --  111.00  45.00  30.00   89
 41  \w     89.00 178.00   1.00    8.00    --  111.00  45.00  60.00   89
 42  \w     81.00 178.00   1.00    8.00    --  111.00  77.00 -30.00   97
 43  \w     85.00 178.00   1.00    8.00    --  111.00  61.00 -30.00   93
 44  \w     85.00 178.00   1.00    8.00    --  111.00  61.00 150.00   93
 45  \w     81.00 178.00   1.00    8.00    --  111.00  77.00-180.00   97
 46  \w     41.00 118.00   1.00    8.00    --  111.00-125.00-180.00   77
 47  \w     81.00 178.00   1.00    8.00    --  111.00  77.00  90.00   97
 48  \w     89.00 178.00   1.00    8.00    --  111.00  45.00 150.00   89
 49  \w     40.00 141.00   1.00    8.00    --  111.00 -77.00 -60.00  101
 50  \w     41.00 118.00   1.00    8.00    --  111.00-125.00 -30.00   77
 51  \w     31.00 110.00   1.00    8.00    --  111.00 -94.00  60.00   79
 52  \w     88.00 178.00   1.00    8.00    --  111.00  47.00 110.31   90
 53  \w   -107.00 -13.00   1.00    2.00    --  -38.50 -57.00 -60.00   94
 54  \w     13.00 114.00   1.00    2.00    --   42.89  77.00  30.00  101
 55  \w     18.00 111.00   1.00    2.00    --   42.89  57.00-120.00   93
 56  \w     22.00 114.00   1.00    2.00    --   42.89  38.00   0.00   92
 57  \w     22.00 114.00   1.00    2.00    --   42.89  38.00  30.00   92
 58  \w     22.00 114.00   1.00    2.00    --   42.89  38.00  90.00   92
 59  \w     22.00 114.00   1.00    2.00    --   42.89  38.00 -90.00   92
 60  \w     18.00 111.00   1.00    2.00    --   42.89  57.00 -30.00   93
 61  \w     18.00 111.00   1.00    2.00    --   42.89  57.00  90.00   93
 62  \w     18.00 111.00   1.00    2.00    --   42.89  57.00 120.00   93
 63  \w     23.00  97.00   1.00    2.00    --   42.89-125.00 -60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0793185000
_diffrn_orient_matrix_UB_12      -0.0774299000
_diffrn_orient_matrix_UB_13      0.0084192000
_diffrn_orient_matrix_UB_21      0.0263964000
_diffrn_orient_matrix_UB_22      0.0507515000
_diffrn_orient_matrix_UB_23      0.0963820000
_diffrn_orient_matrix_UB_31      -0.1029510000
_diffrn_orient_matrix_UB_32      -0.0847676000
_diffrn_orient_matrix_UB_33      0.0049677000
_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  0.0474
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            92149
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.490
_diffrn_reflns_theta_min         2.779
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.599
_exptl_absorpt_correction_T_max  0.529
_exptl_absorpt_correction_T_min  0.116
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       block
_exptl_crystal_F_000             1078
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.074
_refine_diff_density_max         3.385
_refine_diff_density_min         -1.106
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     664
_refine_ls_number_reflns         10372
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0403
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+4.7652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1108
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9927
_reflns_number_total             10372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04441h2.cif
_cod_data_source_block           compound5d
_cod_original_cell_volume        2484.47(7)
_cod_original_formula_sum        'C50.50 H56 N3 O5 P3 W'
_cod_database_code               1552452
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H44 N3 O5 P3 W'
_diffrn_oxdiff_digest_frames
;
01f812d98aa51174b5998ca4360e2754df05809a99c
;
_diffrn_oxdiff_digest_hkl
;
01435365d267d9ddcd7bc7eac9a3e0977f7262
;
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Others
 Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=Sof(C32B)=Sof(H32B)=Sof(C33B)=
 Sof(H33B)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35B)=Sof(H35D)=
 Sof(H35E)=Sof(H35F)=1-FVAR(1)
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 FVAR(1)
 Fixed Sof: C48(0.5) H48(0.5) C49(0.5) H49(0.5) C50(0.5) H50(0.5) C51(0.5)
 H51(0.5) C52(0.5) H52(0.5) C53(0.5) C54(0.5) H54A(0.5) H54B(0.5) H54C(0.5)
3.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20), C29(H29), C29B(H29B),
 C30(H30), C30B(H30B), C32(H32), C32B(H32B), C33(H33), C33B(H33B), C41(H41),
 C42(H42), C43(H43), C44(H44), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51),
  C52(H52)
3.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C34(H34A,H34B,H34C), C34B(H34D,H34E,H34F), C35(H35A,H35B,H35C),
 C35B(H35D,H35E,H35F), C47(H47A,H47B,H47C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              15770
_olex2_date_sample_data_collection 2019-05-21
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.612