Phosphirenium Ions as Masked Phosphenium Catalysts: Mechanistic Evaluation and Application in Synthesis
Gasperini, Danila; Neale, Samuel E.; Mahon, Mary F.; Macgregor, Stuart A.; Webster, Ruth L.; ACS Catalysis  (2021) 5452–5462; doi:10.1021/acscatal.1c01133

data_4518664
_publ_section_title
;
 Phosphirenium Ions as Masked Phosphenium Catalysts: Mechanistic
 Evaluation and Application in Synthesis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5452
_journal_page_last               5462
_journal_paper_doi               10.1021/acscatal.1c01133
_journal_year                    2021
_chemical_formula_moiety         'C26 H20 P, C32 H12 B F24'
_chemical_formula_sum            'C60 H36 B Cl2 F24 P'
_chemical_formula_weight         1325.57
_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     iterative
_audit_creation_date             2019-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.8820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4192(2)
_cell_length_b                   25.9960(4)
_cell_length_c                   18.4476(2)
_cell_measurement_reflns_used    15932
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.6830
_cell_measurement_theta_min      3.3620
_cell_volume                     6297.48(15)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0465
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            63310
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.254
_diffrn_reflns_theta_min         2.980
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.145
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.559
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_description       block
_exptl_crystal_F_000             2664
_exptl_crystal_size_max          0.293
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.168
_refine_diff_density_max         0.608
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     892
_refine_ls_number_reflns         12536
_refine_ls_number_restraints     418
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0670
_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^)+(0.1216P)^2^+2.9417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1944
_refine_ls_wR_factor_ref         0.2087
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9795
_reflns_number_total             12536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01133_si_001.cif
_cod_data_source_block           s18rlw22
_cod_database_code               4518664
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'clear crystals'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F1-C34 \\sim F1A-C34
 with sigma of 0.02
 F2-C34 \\sim F2A-C34
 with sigma of 0.02
 F3-C34 \\sim F3A-C34
 with sigma of 0.02
 F16-C49 \\sim F16A-C49A
 with sigma of 0.02
 F17-C49 \\sim F17A-C49A
 with sigma of 0.02
 F18-C49 \\sim F18A-C49A
 with sigma of 0.02
 C47-C49 \\sim C47-C49A
 with sigma of 0.02
 F16-F17 \\sim F16A-F17A
 with sigma of 0.04
 F16-F18 \\sim F16A-F18A
 with sigma of 0.04
 F16-C47 \\sim F16A-C47
 with sigma of 0.04
 F17-F18 \\sim F17A-F18A
 with sigma of 0.04
 F17-C47 \\sim F17A-C47
 with sigma of 0.04
 F18-C47 \\sim F18A-C47
 with sigma of 0.04
 F13-C50 \\sim F13A-C50A
 with sigma of 0.02
 F14-C50 \\sim F14A-C50A
 with sigma of 0.02
 F15-C50 \\sim F15A-C50A
 with sigma of 0.02
 C45-C50 \\sim C45-C50A
 with sigma of 0.02
 F13-F14 \\sim F13A-F14A
 with sigma of 0.04
 F13-F15 \\sim F13A-F15A
 with sigma of 0.04
 F13-C45 \\sim F13A-C45
 with sigma of 0.04
 F14-F15 \\sim F14A-F15A
 with sigma of 0.04
 F14-C45 \\sim F14A-C45
 with sigma of 0.04
 F15-C45 \\sim F15A-C45
 with sigma of 0.04
 F10-C85 \\sim F10A-C85A
 with sigma of 0.02
 F11-C85 \\sim F11A-C85A
 with sigma of 0.02
 F12-C85 \\sim F12A-C85A
 with sigma of 0.02
 C39-C85 \\sim C39-C85A
 with sigma of 0.02
 F10-F11 \\sim F10A-F11A
 with sigma of 0.04
 F10-F12 \\sim F10A-F12A
 with sigma of 0.04
 F10-C39 \\sim F10A-C39
 with sigma of 0.04
 F11-F12 \\sim F11A-F12A
 with sigma of 0.04
 F11-C39 \\sim F11A-C39
 with sigma of 0.04
 F12-C39 \\sim F12A-C39
 with sigma of 0.04
 F13-F14 \\sim F13-F15 \\sim F14-F15
 with sigma of 0.01
 C50-F13 \\sim C50-F14 \\sim C50-F15
 with sigma of 0.005
 C49-C47 \\sim C49A-C47
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.01
F16 \\sim F17 \\sim F18 \\sim C49 \\sim F16A \\sim F17A \\sim F18A \\sim C49A:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
F13 \\sim F14 \\sim F15 \\sim C50 \\sim F13A \\sim F14A \\sim F15A \\sim C50A:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
F10 \\sim F11 \\sim F12 \\sim C85 \\sim F10A \\sim F11A \\sim F12A \\sim C85A:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: F1(0.55) F2(0.55) F3(0.55) F10(0.2) F11(0.8) F12(0.8) F13(0.5)
 F14(0.5) F15(0.5) F16(0.65) F17(0.65) F18(0.65) C49(0.65) C50(0.5) C85(0.8)
 F1A(0.45) F2A(0.45) F3A(0.45) F10A(0.2) F11A(0.2) F12A(0.8) F13A(0.5)
 F14A(0.5) F15A(0.5) F16A(0.35) F17A(0.35) F18A(0.35) C49A(0.35) C50A(0.5)
 C85A(0.2)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22),
  C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C30(H30), C32(H32),
 C36(H36), C38(H38), C40(H40), C44(H44), C46(H46), C48(H48), C52(H52), C54(H54),
  C56(H56)
;