Di-π-methane rearrangement in 1-phosphabarrelenes: formation and reactivity of an unprecedented 2-phosphasemibullvalene.
Steffen, Leo; Szych, Lilian S.; Franzke, Yannick J.; Kopp, Richard O.; Ernst, Moritz J.; Weber, Manuela; Müller, Christian; Chemical communications (Cambridge, England) 61 (2025) 14907–14910; doi:10.1039/d5cc04015a

data_7134907
_publ_section_title
;
 Di-&#x3c0;-methane rearrangement in 1-phosphabarrelenes: formation and
 reactivity of an unprecedented 2-phosphasemibullvalene.
;
_journal_issue                   77
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14907
_journal_page_last               14910
_journal_paper_doi               10.1039/d5cc04015a
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C23 H17 P Se, C4 H8 O'
_chemical_formula_sum            'C27 H25 O P Se'
_chemical_formula_weight         475.40
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.157(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.3850(6)
_cell_length_b                   13.0349(5)
_cell_length_c                   22.3200(9)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      31.44
_cell_measurement_theta_min      2.63
_cell_volume                     4430.8(3)
_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 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            87352
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.544
_diffrn_reflns_theta_min         2.057
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.784
_exptl_absorpt_correction_T_max  0.6132
_exptl_absorpt_correction_T_min  0.4578
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0830 before and 0.0498 after correction.
The Ratio of minimum to maximum transmission is 0.7466.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.523
_exptl_crystal_size_mid          0.353
_exptl_crystal_size_min          0.268
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         7391
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0296P)^2^+5.6001P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0674
_refine_ls_wR_factor_ref         0.0712
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6433
_reflns_number_total             7391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04015a2.cif
_cod_data_source_block           leo045_mje
_cod_depositor_comments
'Adding full bibliography for 7134904--7134908.cif.'
_cod_database_code               7134907
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C102(H10C,H10D), C103(H10E,H10F), C104(H10G,H10H)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
;
_shelx_res_checksum              71251
_shelx_hkl_checksum              77057
_olex2_submission_special_instructions 'No special instructions were received'