Phosphinoborenium cations stabilized by N-heterocyclic carbenes: synthesis, structure, and reactivity
Kaniewska-Laskowska, Kinga; Ordyszewska, Anna; Wojnowski, Tomasz; Halenka, Hanna; Czapla, Marcin; Chojnacki, Jarosław; Grubba, Rafał; Dalton Transactions  (2023) –; doi:10.1039/D3DT03090C

data_7714198
_publ_section_title
;
 Phosphinoborenium cations stabilized by N-heterocyclic carbenes:
 synthesis, structure, and reactivity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03090C
_journal_year                    2023
_chemical_formula_moiety
'2(C16 Al F36 O4 -), 2(C28 H64 Au B2 Br2 N2 P2 +), 3(C7 H8)'
_chemical_formula_sum            'C109 H152 Al2 Au2 B4 Br4 F72 N4 O8 P4'
_chemical_formula_weight         3948.99
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-07-19 deposited with the CCDC.	2023-10-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.128(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.8390(11)
_cell_length_b                   23.5598(8)
_cell_length_c                   26.1742(12)
_cell_measurement_reflns_used    36507
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.87
_cell_measurement_theta_min      1.98
_cell_volume                     15314.2(11)
_computing_cell_refinement       'X-Area Recipe 1.34.0.0 (STOE, 2019)'
_computing_data_collection       'X-Area WinXpose 2.0.22.0 (STOE, 2016)'
_computing_data_reduction
'X-Area Integrate 1.77.0.0 (STOE, 2019) X-Area X-Red32 1.65.0.0 (STOE, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean 6.67
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            158079
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.900
_diffrn_reflns_theta_min         2.060
_diffrn_source                   'GeniX Mo, 0.05 x 0.05 mm2 microfocus'
_exptl_absorpt_coefficient_mu    3.148
_exptl_absorpt_correction_T_max  0.6824
_exptl_absorpt_correction_T_min  0.4540
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
'STOE X-Red32, absorption correction by Gaussian integration, analogous to P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis", published in F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard, Copenhagen (1970), 255 - 270'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.713
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             7800
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.326
_refine_diff_density_min         -1.167
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2066
_refine_ls_number_reflns         33063
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      1.176
_refine_ls_R_factor_all          0.0910
_refine_ls_R_factor_gt           0.0636
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+212.7075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1380
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24985
_reflns_number_total             33063
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03090c2.cif
_cod_data_source_block           1d
_cod_database_code               7714198
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.650
_shelx_estimated_absorpt_t_min   0.432
_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. Restrained distances
 C77-C78 = C77-C79 = C77-C80
 1.555 with sigma of 0.02
 C78-F49 = C78-F50 = C78-F51
 1.328 with sigma of 0.02
 C79-F46 = C79-F47 = C79-F48
 1.328 with sigma of 0.02
 C80-F52 = C80-F53 = C80-F54
 1.328 with sigma of 0.02
 C77-C78A = C77-C79A = C77-C80A
 1.555 with sigma of 0.02
 C78A-F50A = C78A-F51A
 1.328 with sigma of 0.02
 C79A-F46A = C79A-F47A = C79A-F48A
 1.328 with sigma of 0.02
 C80A-F52A = C80A-F53A = C80A-F54A
 1.328 with sigma of 0.02
 C77-F46A = C77-F47A = C77-F48A
 2.38 with sigma of 0.02
 C77-F49A = C77-F50A = C77-F51A
 2.38 with sigma of 0.02
 C77-F52A = C77-F53A = C77-F54A
 2.38 with sigma of 0.02
 C85-C86 = C85-C87 = C85-C88
 1.555 with sigma of 0.02
 C86-F64 = C86-F65 = C86-F66
 1.328 with sigma of 0.02
 C87-F67 = C87-F68 = C87-F69
 1.328 with sigma of 0.02
 C88-F70 = C88-F71 = C88-F72
 1.328 with sigma of 0.02
 C86A-F64A = C86A-F65A = C86A-F66A
 1.328 with sigma of 0.02
 C87A-F67A = C87A-F68A = C87A-F69A
 1.328 with sigma of 0.02
 C88A-F70A = C88A-F71A = C88A-F72A
 1.328 with sigma of 0.02
 C85-C86A = C85-C87A = C85-C88A
 1.555 with sigma of 0.02
 C85-F64A = C85-F65A = C85-F66A
 2.38 with sigma of 0.02
 C85-F67A = C85-F68A = C85-F69A
 2.38 with sigma of 0.02
 C85-F70A = C85-F71A = C85-F72A
 2.38 with sigma of 0.02
 F70-F71 \\sim F71-F72 \\sim F72-F70
 with sigma of 0.02
 C86-C87 \\sim C87-C88 \\sim C88-C86
 with sigma of 0.02
 C86A-C87A \\sim C87A-C88A \\sim C88A-C86A
 with sigma of 0.02
 F37-C74 \\sim F37A-C74A
 with sigma of 0.02
 F38-C74 \\sim F38A-C74A
 with sigma of 0.02
 F39-C74 \\sim F39A-C74A
 with sigma of 0.02
 F40-C75 \\sim F40A-C75A
 with sigma of 0.02
 F41-C75 \\sim F41A-C75A
 with sigma of 0.02
 F42-C75 \\sim F42A-C75A
 with sigma of 0.02
 F43-C76 \\sim F43A-C76A
 with sigma of 0.02
 F44-C76 \\sim F44A-C76A
 with sigma of 0.02
 F45-C76 \\sim F45A-C76A
 with sigma of 0.02
 O5-C73 \\sim O5-C73A
 with sigma of 0.04
 C73-C74 \\sim C73A-C74A
 with sigma of 0.02
 C73-C75 \\sim C73A-C75A
 with sigma of 0.02
 C73-C76 \\sim C73A-C76A
 with sigma of 0.02
 F37-F38 \\sim F37A-F38A \\sim F37-F39 \\sim F37A-F39A
 with sigma of 0.04
 F38-F39 \\sim F38A-F39A
 with sigma of 0.04
 F40-F41 \\sim F40A-F41A \\sim F40-F42 \\sim F40A-F42A
 with sigma of 0.04
 F41-F42 \\sim F41A-F42A
 with sigma of 0.04
 F45-F43 \\sim F45A-F43A
 with sigma of 0.04
 F45-F44 \\sim F45A-F44A
 with sigma of 0.04
 F43-F44 \\sim F43A-F44A
 with sigma of 0.04
 O5-C74 \\sim O5-C74A
 with sigma of 0.04
 O5-C75 \\sim O5-C75A
 with sigma of 0.04
 O5-C76 \\sim O5-C76A
 with sigma of 0.04
 C74-C75 \\sim C74A-C75A
 with sigma of 0.04
 C74-C76 \\sim C74A-C76A
 with sigma of 0.04
 C75-C76 \\sim C75A-C76A
 with sigma of 0.04
 C103-C104 \\sim C104-C105 \\sim C105-C106 \\sim C106-C107 \\sim C107-C108
\\sim C108-C103
 with sigma of 0.04
 O6-C77 \\sim O6A-C77A
 with sigma of 0.02
 Al2-O5 \\sim Al2-O5A
 with sigma of 0.02
3. Rigid bond restraints
 F48, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F49, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F65 \\sim F64: within 3.5A with sigma of 0.03 and sigma for terminal atoms of
0.06
O6 \\sim O6A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
O5 \\sim O5A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F71 \\sim F70: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F41 \\sim F45: within 2.95A with sigma of 0.03 and sigma for terminal atoms of
0.06
Uanis(C73) = Uanis(C73A)
5. Others
 Sof(F46A)=Sof(F47A)=Sof(F48A)=Sof(F49A)=Sof(F50A)=Sof(F51A)=Sof(F52A)=
 Sof(F53A)=Sof(F54A)=Sof(O6A)=Sof(C77A)=Sof(C78A)=Sof(C79A)=Sof(C80A)=1-FVAR(1)
 Sof(F46)=Sof(F47)=Sof(F48)=Sof(F49)=Sof(F50)=Sof(F51)=Sof(F52)=Sof(F53)=
 Sof(F54)=Sof(O6)=Sof(C77)=Sof(C78)=Sof(C79)=Sof(C80)=FVAR(1)
 Sof(F64A)=Sof(F65A)=Sof(F66A)=Sof(F67A)=Sof(F68A)=Sof(F69A)=Sof(F70A)=
 Sof(F71A)=Sof(F72A)=Sof(C86A)=Sof(C87A)=Sof(C88A)=1-FVAR(2)
 Sof(F64)=Sof(F65)=Sof(F66)=Sof(F67)=Sof(F68)=Sof(F69)=Sof(F70)=Sof(F71)=
 Sof(F72)=Sof(C86)=Sof(C87)=Sof(C88)=FVAR(2)
 Sof(F37A)=Sof(F38A)=Sof(F39A)=Sof(F40A)=Sof(F41A)=Sof(F42A)=Sof(F43A)=
 Sof(F44A)=Sof(F45A)=Sof(O5A)=Sof(C73A)=Sof(C74A)=Sof(C75A)=Sof(C76A)=1-FVAR(3)
 Sof(F37)=Sof(F38)=Sof(F39)=Sof(F40)=Sof(F41)=Sof(F42)=Sof(F43)=Sof(F44)=
 Sof(F45)=Sof(O5)=Sof(C73)=Sof(C74)=Sof(C75)=Sof(C76)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C15(H15), C18(H18), C45(H45), C48(H48), C59(H59), C62(H62)
6.b Me refined with riding coordinates:
 C102(H10D,H10E,H10F)
6.c Aromatic/amide H refined with riding coordinates:
 C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C97(H97), C98(H98),
 C99(H99), C100(H100), C101(H101), C104(H104), C105(H105), C106(H106),
 C107(H107), C108(H108)
6.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,
 H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,
 H60B,H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C95(H95A,H95B,H95C),
 C109(H10G,H10H,H10I)
;
_shelx_res_checksum              80706
_olex2_submission_special_instructions 'No special instructions were received'