The bismuth phosphanides Bi(PR<sub>2</sub>)<sub>3</sub>: sources of phosphanyl radicals, P-inversion, and reversible olefin insertion.
Reith, Sascha; Oberdorf, Kai; Martínez, Sebstián; Landgraf, Jann B.; Ahrens, Alena; Jakobi, Felix; Xie, Xiulan; Lichtenberg, Crispin; Chemical science 17 (2026) 5183–5191; doi:10.1039/d5sc07240a

data_1576867
_publ_section_title
;
 The bismuth phosphanides Bi(PR<sub>2</sub>)<sub>3</sub>: sources of
 phosphanyl radicals, P-inversion, and reversible olefin insertion.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              5183
_journal_page_last               5191
_journal_paper_doi               10.1039/d5sc07240a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C17 H36 P2 S2'
_chemical_formula_sum            'C17 H36 P2 S2'
_chemical_formula_weight         366.52
_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             2025-11-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-11-11 deposited with the CCDC.	2025-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                105.127(2)
_cell_angle_beta                 90.987(2)
_cell_angle_gamma                95.913(2)
_cell_formula_units_Z            3
_cell_length_a                   8.7077(4)
_cell_length_b                   12.9666(6)
_cell_length_c                   14.9308(7)
_cell_measurement_reflns_used    9320
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      29.444
_cell_measurement_theta_min      2.430
_cell_volume                     1617.04(13)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Apex-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            123184
_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         30.051
_diffrn_reflns_theta_min         1.859
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.390
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.7237
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0767 before and 0.0522 after correction.
The Ratio of minimum to maximum transmission is 0.9701.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.129
_exptl_crystal_description       needle
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.86
_exptl_crystal_size_mid          0.78
_exptl_crystal_size_min          0.293
_refine_diff_density_max         1.599
_refine_diff_density_min         -0.650
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.190
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         9439
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.192
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0533
_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^)+(0.0287P)^2^+2.0020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1210
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9083
_reflns_number_total             9439
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07240a2.cif
_cod_data_source_block           srpx20a_1
_cod_database_code               1576867
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.730
_olex2_refinement_description
;
1. Restrained distances
 P2-C0 \\sim P1-C1
 with sigma of 0.02
 S2A-C0 \\sim S2-C1
 with sigma of 0.02
 S1A-C0 \\sim S1-C1
 with sigma of 0.02
2. Others
 Sof(S3A)=0.5*(1-FVAR(2))
 Sof(S3)=0.5*FVAR(2)
 Sof(S1A)=Sof(S2A)=Sof(C0)=1-FVAR(2)
 Sof(S2)=Sof(S1)=Sof(C1)=FVAR(2)
 Fixed Sof: C18(0.5) S4(0.5)
3.a Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C11(H11A,H11B,
 H11C), C22(H22A,H22B,H22C), C5(H5A,H5B,H5C), C17(H17A,H17B,H17C), C9(H9A,H9B,
 H9C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C8(H8A,H8B,H8C), C16(H16A,H16B,
 H16C), C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C26(H26A,H26B,
 H26C), C21(H21A,H21B,H21C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              24553
_olex2_submission_special_instructions 'No special instructions were received'