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_1552449
_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_absolute_configuration ad
_chemical_formula_moiety         'C34 H41 N2 P3, C7 H8'
_chemical_formula_sum            'C41 H49 N2 P3'
_chemical_formula_weight         662.73
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-10 deposited with the CCDC.    2019-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1499(5)
_cell_length_b                   17.6614(8)
_cell_length_c                   19.2232(6)
_cell_measurement_reflns_used    14670
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      76.1140
_cell_measurement_theta_min      3.3750
_cell_volume                     3785.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      100.0(1)
_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 0.982
_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   -122.00 -35.00   1.00    8.00    --  -38.50-178.00  30.00   87
  2  \w   -110.00 -18.00   1.00    8.00    --  -38.50 -38.00 150.00   92
  3  \w   -123.00 -34.00   1.00    8.00    --  -38.50 178.00 150.00   89
  4  \w     57.00 127.00   1.00    8.00    --   43.20 178.00  90.00   70
  5  \w     85.00 178.00   1.00   32.00    --  111.00  61.00 120.00   93
  6  \w     31.00 110.00   1.00   32.00    --  111.00 -94.00  60.00   79
  7  \w     94.00 178.00   1.00   32.00    --  111.00 125.00 -90.00   84
  8  \w     81.00 178.00   1.00   32.00    --  111.00  77.00-180.00   97
  9  \w     41.00 118.00   1.00   32.00    --  111.00-125.00 -30.00   77
 10  \w     41.00 118.00   1.00   32.00    --  111.00-125.00-150.00   77
 11  \w     31.00 110.00   1.00   32.00    --  111.00 -94.00-180.00   79
 12  \w     90.00 178.00   1.00   32.00    --  111.00  30.00-120.00   88
 13  \w     13.00 115.00   1.00    8.00    --   43.20  77.00   0.00  102
 14  \w     18.00 112.00   1.00    8.00    --   43.20  57.00 120.00   94
 15  \w     18.00 112.00   1.00    8.00    --   43.20  57.00 -90.00   94
 16  \w     71.00 141.00   1.00   32.00    --  111.00  15.00  60.00   70
;
_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      0.1152783000
_diffrn_orient_matrix_UB_12      0.0073722000
_diffrn_orient_matrix_UB_13      -0.0436866000
_diffrn_orient_matrix_UB_21      0.0416141000
_diffrn_orient_matrix_UB_22      0.0665810000
_diffrn_orient_matrix_UB_23      0.0460297000
_diffrn_orient_matrix_UB_31      0.0637426000
_diffrn_orient_matrix_UB_32      -0.0558597000
_diffrn_orient_matrix_UB_33      0.0489742000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            31369
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.768
_diffrn_reflns_theta_min         3.398
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.659
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.855
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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 brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1416
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.087
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2682 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(12)
_refine_ls_extinction_coef       0.00082(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7770
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0509
_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^)+(0.0492P)^2^+2.6152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1214
_refine_ls_wR_factor_ref         0.1253
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                7012
_reflns_number_total             7770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04441h2.cif
_cod_data_source_block           compound4c
_cod_database_code               1552449
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C41H49N2P3
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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(C35B)=Sof(C36B)=Sof(H36B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38B)=
 Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=Sof(C41B)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=1-FVAR(1)
 Sof(C35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=Sof(C41A)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C17(H17), C20(H20), C29(H29), C32(H32)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C13(H13), C14(H14), C15(H15), C25(H25),
 C26(H26), C27(H27), C36A(H36A), C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A),
  C36B(H36B), C37B(H37B), C38B(H38B), C39B(H39B), C40B(H40B)
3.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C41A(H41A,H41B,H41C), C41B(H41D,H41E,H41F)
;
_shelx_res_checksum              31519
_olex2_date_sample_data_collection 2018-10-22
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.189
_oxdiff_exptl_absorpt_empirical_full_min 0.847