Carbodiphosphorane mediated synthesis of a triflyloxyphosphonium dication and its reactivity towards nucleophiles.
Yogendra, S.; Hennersdorf, F.; Bauzá, A; Frontera, A.; Fischer, R.; Weigand, J. J.; Chemical communications (Cambridge, England) 53 (2017) 2954–2957; doi:10.1039/c7cc00982h

data_7119766
_publ_section_title
;
 Carbodiphosphorane mediated synthesis of a triflyloxyphosphonium dication
 and its reactivity towards nucleophiles.
;
_journal_issue                   20
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2954
_journal_page_last               2957
_journal_paper_doi               10.1039/c7cc00982h
_journal_volume                  53
_journal_year                    2017
_chemical_formula_moiety         'C50 H40 N P3 S, 2(C F3 O3 S), 1.5(C6 H5 F)'
_chemical_formula_sum            'C61 H47.5 F7.5 N O6 P3 S3'
_chemical_formula_weight         1222.09
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-11-15 deposited with the CCDC.
2017-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0535(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3116(2)
_cell_length_b                   21.2851(3)
_cell_length_c                   19.4915(3)
_cell_measurement_reflns_used    33224
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.3490
_cell_measurement_theta_min      3.0660
_cell_volume                     5514.86(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -65.00  32.00   0.50    5.00    --  -38.50  57.00 -60.00  194
  2  \w   -109.00 -12.00   0.50    5.00    --  -38.50 -57.00 150.00  194
  3  \w     20.00 115.00   0.50    5.00    --   42.50  38.00  60.00  190
  4  \w     23.00  98.00   0.50    5.00    --   42.50-125.00-180.00  150
  5  \w     30.00 109.00   0.50   20.00    --  111.00 -94.00 150.00  158
  6  \w     83.00 178.00   0.50   20.00    --  111.00  61.00  90.00  190
  7  \w     94.00 178.00   0.50   20.00    --  111.00 125.00-180.00  168
  8  \w     39.00 121.00   0.50   20.00    --  111.00-125.00-120.00  164
  9  \w     30.00 109.00   0.50   20.00    --  111.00 -94.00  60.00  158
 10  \w     87.00 178.00   0.50   20.00    --  111.00  45.00   0.00  182
 11  \w     94.00 178.00   0.50   20.00    --  111.00 125.00-150.00  168
 12  \w     40.00 135.00   0.50   20.00    --  111.00 -45.00 120.00  190
 13  \w     87.00 178.00   0.50   20.00    --  111.00  45.00-180.00  182
 14  \w     30.00 109.00   0.50   20.00    --  111.00 -94.00 120.00  158
 15  \w     87.00 178.00   0.50   20.00    --  111.00  45.00 120.00  182
 16  \w     30.00 109.00   0.50   20.00    --  111.00 -94.00 -30.00  158
 17  \w     43.00 121.00   0.50   20.00    --  111.00-125.00 -60.00  156
 18  \w     87.00 121.00   0.50   20.00    --  111.00 -61.00 -90.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0503653000
_diffrn_orient_matrix_UB_12      0.0599150000
_diffrn_orient_matrix_UB_13      0.0298929000
_diffrn_orient_matrix_UB_21      0.1035174000
_diffrn_orient_matrix_UB_22      -0.0323236000
_diffrn_orient_matrix_UB_23      -0.0002145000
_diffrn_orient_matrix_UB_31      0.0134841000
_diffrn_orient_matrix_UB_32      0.0245438000
_diffrn_orient_matrix_UB_33      -0.0732945000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            51985
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.567
_diffrn_reflns_theta_min         3.077
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.741
_exptl_absorpt_correction_T_max  0.835
_exptl_absorpt_correction_T_min  0.661
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_description       block
_exptl_crystal_F_000             2516
_exptl_crystal_size_max          0.215
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.368
_refine_diff_density_min         -1.123
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     991
_refine_ls_number_reflns         11521
_refine_ls_number_restraints     868
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0996
_refine_ls_R_factor_gt           0.0992
_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^)+(0.0515P)^2^+28.8478P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2250
_refine_ls_wR_factor_ref         0.2252
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11393
_reflns_number_total             11521
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc00982h2.cif
_cod_data_source_block           10OTf2
_cod_original_cell_volume        5514.87(15)
_cod_original_formula_sum        'C61 H47.50 F7.50 N O6 P3 S3'
_cod_database_code               7119766
_chemical_oxdiff_formula         'C52 H40 F6 N O6 P3 S3'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 P1B-C1 \\sim P1A-C1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O3A \\sim F2A \\sim C51A \\sim F1A \\sim F3A \\sim S2A \\sim O2A \\sim O1A
\\sim S2B \\sim F2B \\sim C51B \\sim F1B \\sim F3B \\sim O1B \\sim O3B \\sim
O2B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O6B \\sim F5B \\sim C52B \\sim F6B \\sim F4B \\sim S3B \\sim O5B \\sim O4B
\\sim O6A \\sim F5A \\sim C52A \\sim F6A \\sim F4A \\sim S3A \\sim O4A \\sim
O5A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C60 \\sim C59 \\sim C64 \\sim F8 \\sim C61 \\sim C63 \\sim C62: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
P1A \\sim S1A \\sim C50A \\sim N1A \\sim C8A \\sim C9A \\sim C10A \\sim C11A
\\sim C12A \\sim C13A \\sim S1B \\sim C50B \\sim N1B \\sim C8B \\sim C9B \\sim
C10B \\sim C11B \\sim C12B \\sim C13B \\sim P1B: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04
4. Same fragment restrains
{S1B, C50B, N1B, P1B, C8B, C9B, C10B, C11B, C12B, C13B} sigma for 1-2: 0.02,
1-3: 0.02
as
{S1A, C50A, N1A, P1A, C8A, C9A, C10A, C11A, C12A, C13A}
{F2B, F1B, F3B, C51B, S2B, O1B, O3B, O2B} sigma for 1-2: 0.02, 1-3: 0.02
{F5A, F6A, F4A, C52A, S3A, O5A, O6A, O4A} sigma for 1-2: 0.02, 1-3: 0.02
{F5B, F6B, F4B, C52B, S3B, O5B, O6B, O4B} sigma for 1-2: 0.02, 1-3: 0.02
as
{F2A, F1A, F3A, C51A, S2A, O2A, O1A, O3A}
5. Others
 Sof(F5B)=Sof(F6B)=Sof(F4B)=Sof(C52B)=Sof(S3B)=Sof(O5B)=Sof(O6B)=Sof(O4B)=1-
 FVAR(1)
 Sof(F5A)=Sof(F6A)=Sof(F4A)=Sof(C52A)=Sof(S3A)=Sof(O5A)=Sof(O6A)=Sof(O4A)=
 FVAR(1)
 Sof(S1B)=Sof(C50B)=Sof(N1B)=Sof(P1B)=Sof(C8B)=Sof(C9B)=Sof(H9B)=Sof(C10B)=
 Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=1-FVAR(2)
 Sof(S1A)=Sof(C50A)=Sof(N1A)=Sof(P1A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=FVAR(2)
 Sof(F2B)=Sof(F1B)=Sof(F3B)=Sof(C51B)=Sof(S2B)=Sof(O1B)=Sof(O3B)=Sof(O2B)=1-
 FVAR(3)
 Sof(F2A)=Sof(F1A)=Sof(F3A)=Sof(C51A)=Sof(S2A)=Sof(O2A)=Sof(O1A)=Sof(O3A)=
 FVAR(3)
 Fixed Sof: C59(0.5) C60(0.5) H60(0.5) C61(0.5) H61(0.5) C62(0.5) H62(0.5)
 C63(0.5) H63(0.5) C64(0.5) H64(0.5) F8(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A), C37(H37), C43(H43),
 C45(H45), C15(H15), C19(H19), C49(H49), C25(H25), C41(H41), C16(H16), C39(H39),
  C33(H33), C18(H18), C27(H27), C40(H40), C46(H46), C17(H17), C42(H42),
 C35(H35), C21(H21), C7(H7), C31(H31), C34(H34), C6(H6), C22(H22), C28(H28),
 C36(H36), C48(H48), C3(H3), C24(H24), C23(H23), C4(H4), C30(H30), C5(H5),
 C47(H47), C29(H29), C58(H58), C54(H54), C57(H57), C55(H55), C60(H60), C61(H61),
  C62(H62), C63(H63), C64(H64), C56(H56), C9B(H9B), C10B(H10B), C11B(H11B),
 C12B(H12B), C13B(H13B)
6.b Fitted hexagon refined as free rotating group:
 C59(C60,C61,C62,C63,C64)
;
_shelx_res_checksum              35071
_shelx_shelxl_version_number     2014/7
_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 2.033
_oxdiff_exptl_absorpt_empirical_full_min 0.807