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_7134906
_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         'C25 H21 P'
_chemical_formula_sum            'C25 H21 P'
_chemical_formula_weight         352.39
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-09
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.776(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0080(6)
_cell_length_b                   16.5827(16)
_cell_length_c                   16.2271(15)
_cell_measurement_reflns_used    9652
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      72.82
_cell_measurement_theta_min      5.34
_cell_volume                     1884.9(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0874
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            17691
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.568
_diffrn_reflns_theta_max         66.568
_diffrn_reflns_theta_min         3.812
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.303
_exptl_absorpt_correction_T_max  0.5482
_exptl_absorpt_correction_T_min  0.2617
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1892 before and 0.1114 after correction.
The Ratio of minimum to maximum transmission is 0.4774.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_description       needle
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.64
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3300
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0870
_refine_ls_R_factor_gt           0.0673
_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^)+(0.1189P)^2^+1.1082P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1769
_refine_ls_wR_factor_ref         0.1923
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2553
_reflns_number_total             3300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04015a2.cif
_cod_data_source_block           leo95_a
_cod_depositor_comments
'Adding full bibliography for 7134904--7134908.cif.'
_cod_database_code               7134906
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.489
_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.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C20(H20), C21(H21), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              41697
_shelx_hkl_checksum              94192
_olex2_submission_special_instructions 'No special instructions were received'