Hidden Silylium-Type Reactivity of a Siloxane-Based Phosphonium–Hydroborate Ion Pair
Fontana, Nicolò; Espinosa-Jalapa, Noel Angel; Seidl, Michael; Bauer, Jonathan O.; Chemical Communications  (2022) –; doi:10.1039/D1CC07016A

data_7129584
_publ_section_title
;
 Hidden Silylium-Type Reactivity of a Siloxane-Based
 Phosphonium--Hydroborate Ion Pair
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC07016A
_journal_year                    2022
_chemical_formula_moiety         'C31 H44 O P S Si2, B C24 F20'
_chemical_formula_sum            'C55 H44 B F20 O P S Si2'
_chemical_formula_weight         1230.92
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-14
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.06.29 svn.r12e2184c for OlexSys, GUI svn.r6374)
;
_audit_update_record
;
2021-09-02 deposited with the CCDC.	2022-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                101.2990(10)
_cell_angle_beta                 90.3210(10)
_cell_angle_gamma                93.8460(10)
_cell_formula_units_Z            2
_cell_length_a                   9.9141(2)
_cell_length_b                   14.3805(2)
_cell_length_c                   19.1892(3)
_cell_measurement_reflns_used    23003
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      66.4750
_cell_measurement_theta_min      4.2760
_cell_volume                     2676.24(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.993
_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    -68.00 -42.00   1.00    5.00    --  -42.98  78.00  22.00   26
  2  \w     -5.00  20.00   1.00    5.00    --  -42.98  78.00  22.00   25
  3  \w    -30.00  36.00   1.00    5.00    --   42.98 -78.00-102.00   66
  4  \w     49.00  75.00   1.00    5.00    --   42.98 -78.00-102.00   26
  5  \w     41.00  66.00   1.00   30.00    --   86.50 -78.00-102.00   25
  6  \w   -163.00-114.00   1.00   30.00    --  -90.00 -78.00-102.00   49
  7  \w    -93.00 -29.00   1.00    5.00    --  -42.98 125.00 150.00   64
  8  \w     42.00 113.00   1.00    5.00    --   42.98  57.00  30.00   71
  9  \w     29.00 107.00   1.00    5.00    --   42.98  57.00 -30.00   78
 10  \w     96.00 121.00   1.00   30.00    --   86.50  78.00  22.00   25
 11  \w   -112.00 -55.00   1.00   30.00    --  -90.00 125.00 150.00   57
 12  \w   -105.00 -35.00   1.00   30.00    --  -90.00 125.00  30.00   70
 13  \w   -164.00-103.00   1.00   30.00    --  -90.00 -77.00   0.00   61
 14  \w   -106.00 -67.00   1.00   30.00    --  -90.00 110.00  15.87   39
 15  \w    -68.00 -42.00   1.00   30.00    --  -90.00  15.00  60.00   26
 16  \w    -60.00 -15.00   1.00   30.00    --  -90.00 110.00  15.87   45
 17  \w   -173.00-147.00   1.00   30.00    --  -90.00 -94.00-120.00   26
 18  \w    -99.00 -28.00   1.00   30.00    --  -90.00 125.00-180.00   71
 19  \w   -112.00 -51.00   1.00   30.00    --  -90.00 125.00  60.00   61
 20  \w    -67.00 -42.00   1.00   30.00    --  -90.00  45.00  30.00   25
 21  \w    -63.00 -31.00   1.00   30.00    --  -90.00  99.00-174.74   32
 22  \w   -116.00 -62.00   1.00   30.00    --  -90.00  61.00 -30.00   54
 23  \w   -163.00-132.00   1.00   30.00    --  -90.00 -77.00  60.00   31
 24  \w   -107.00 -30.00   1.00   30.00    --  -90.00 125.00 -90.00   77
 25  \w   -125.00 -97.00   1.00   30.00    --  -90.00-125.00 -30.00   28
 26  \w   -145.00-107.00   1.00   30.00    --  -90.00 -77.00 150.00   38
 27  \w   -131.00-105.00   1.00   30.00    --  -90.00 151.00-103.36   26
 28  \w    -90.00 -32.00   1.00   30.00    --  -90.00  53.00 -98.49   58
 29  \w   -110.00 -85.00   1.00   30.00    --  -90.00 -45.00  90.00   25
 30  \w   -138.00-113.00   1.00   30.00    --  -90.00 -94.00-120.00   25
 31  \w    -94.00 -42.00   1.00   30.00    --  -90.00 125.00  90.00   52
 32  \w   -105.00 -80.00   1.00   30.00    --  -90.00  77.00  60.00   25
 33  \w    -72.00 -46.00   1.00   30.00    --  -90.00  77.00  60.00   26
 34  \w   -122.00 -92.00   1.00   30.00    --  -90.00  83.00  10.63   30
 35  \w    -42.00 -17.00   1.00   30.00    --  -90.00  83.00  10.63   25
 36  \w   -144.00-104.00   1.00   30.00    --  -90.00 -94.00  41.29   40
 37  \w   -142.00-116.00   1.00   30.00    --  -90.00-125.00  30.00   26
 38  \w    -72.00 -47.00   1.00   30.00    --  -90.00  86.00 -35.32   25
 39  \w   -121.00 -96.00   1.00   30.00    --  -90.00  86.00 -35.32   25
 40  \w   -164.00-138.00   1.00   30.00    --  -90.00-125.00 -60.00   26
 41  \w   -125.00 -98.00   1.00   30.00    --  -90.00-125.00 -60.00   27
 42  \w   -107.00 -31.00   1.00   30.00    --  -90.00 125.00 120.00   76
 43  \w    -77.00 -31.00   1.00   30.00    --  -90.00  45.00 -30.00   46
 44  \w   -107.00 -66.00   1.00   30.00    --  -90.00 -61.00   0.00   41
 45  \w    -61.00 -26.00   1.00   30.00    --  -90.00  30.00 -30.00   35
 46  \w   -157.00-131.00   1.00   30.00    --  -90.00 -77.00 120.00   26
 47  \w   -162.00-110.00   1.00   30.00    --  -90.00-125.00-180.00   52
 48  \w   -162.00-128.00   1.00   30.00    --  -90.00-125.00   0.00   34
 49  \w    -69.00 -37.00   1.00   30.00    --  -90.00 125.00-150.00   32
 50  \w   -143.00-117.00   1.00   30.00    --  -90.00 -45.00-150.00   26
 51  \w    -93.00 -66.00   1.00   30.00    --  -90.00 -45.00  60.00   27
 52  \w   -160.00-126.00   1.00   30.00    --  -90.00 -45.00  90.00   34
 53  \w   -115.00 -73.00   1.00   30.00    --  -90.00  15.00  60.00   42
 54  \w   -107.00 -82.00   1.00   30.00    --  -90.00  61.00-120.00   25
 55  \w   -108.00 -82.00   1.00   30.00    --  -90.00 103.00 -80.98   26
 56  \w    -76.00 -51.00   1.00   30.00    --  -90.00  96.00  79.02   25
 57  \w    -98.00 -73.00   1.00   30.00    --  -90.00  89.00 149.38   25
 58  \w    -38.00 -13.00   1.00   30.00    --  -90.00  89.00 149.38   25
 59  \w    -45.00 -20.00   1.00   30.00    --  -90.00  30.00 -60.00   25
 60  \w    -87.00 -62.00   1.00   30.00    --  -90.00  27.00 178.81   25
 61  \w    -97.00 -71.00   1.00   30.00    --  -90.00  78.00  22.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1061468000
_diffrn_orient_matrix_UB_12      -0.0420058000
_diffrn_orient_matrix_UB_13      -0.0532908000
_diffrn_orient_matrix_UB_21      0.1120107000
_diffrn_orient_matrix_UB_22      0.0650697000
_diffrn_orient_matrix_UB_23      0.0444414000
_diffrn_orient_matrix_UB_31      0.0212332000
_diffrn_orient_matrix_UB_32      -0.0774213000
_diffrn_orient_matrix_UB_33      0.0434759000
_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  0.0812
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            41863
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.647
_diffrn_reflns_theta_max         66.647
_diffrn_reflns_theta_min         4.278
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.247
_exptl_absorpt_correction_T_max  0.714
_exptl_absorpt_correction_T_min  0.607
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.90a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             1252
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/pentane'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     739
_refine_ls_number_reflns         9402
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0491
_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^)+(0.0804P)^2^+1.5416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1286
_refine_ls_wR_factor_ref         0.1342
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8248
_reflns_number_total             9402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc07016a2.cif
_cod_data_source_block           nf_693_1_ap_abs_ana
_cod_database_code               7129584
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C55H44BF20OPSSi2
_shelx_estimated_absorpt_t_max   0.650
_shelx_estimated_absorpt_t_min   0.507
_reflns_odcompleteness_completeness 98.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C21(H21), C11(H11), C15(H15), C13(H13), C12(H12), C27(H27),
 C17(H17), C23(H23), C20(H20), C19(H19), C26(H26), C18(H18), C25(H25), C24(H24)
2.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C29(H29A,H29B,H29C), C9(H9A,H9B,H9C), C5(H5A,H5B,H5C),
 C8(H8A,H8B,H8C), C31(H31A,H31B,H31C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C7(H7A,
 H7B,H7C)
;
_shelx_res_checksum              54259
_shelx_hkl_checksum              38005
_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 4.145
_oxdiff_exptl_absorpt_empirical_full_min 0.097