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_7134908
_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         'C50 H42 P2, C H2 Cl2'
_chemical_formula_sum            'C51 H44 Cl2 P2'
_chemical_formula_weight         789.70
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2025-05-27
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                74.530(2)
_cell_angle_beta                 89.830(2)
_cell_angle_gamma                72.660(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7787(7)
_cell_length_b                   12.1311(6)
_cell_length_c                   15.4644(8)
_cell_measurement_reflns_used    9722
_cell_measurement_temperature    144.00
_cell_measurement_theta_max      28.68
_cell_measurement_theta_min      2.35
_cell_volume                     2025.80(19)
_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      144.00
_diffrn_measured_fraction_theta_full 0.998
_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  0.0406
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            88958
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.709
_diffrn_reflns_theta_min         2.146
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.275
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6374
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1043 before and 0.0695 after correction.
The Ratio of minimum to maximum transmission is 0.8547.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.404
_exptl_crystal_size_mid          0.264
_exptl_crystal_size_min          0.259
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         10431
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0362P)^2^+1.4074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0876
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9496
_reflns_number_total             10431
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04015a2.cif
_cod_data_source_block           leo95_ls4_mje
_cod_depositor_comments
'Adding full bibliography for 7134904--7134908.cif.'
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7134908
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.897
_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 Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C22(H22), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C11(H11), C23(H23), C28(H28), C29(H29),
 C30(H30), C31(H31), C42(H42), C43(H43), C45(H45), C46(H46), C52(H52), C53(H53),
  C55(H55), C56(H56), C62(H62), C63(H63), C65(H65), C66(H66), C72(H72),
 C73(H73), C75(H75), C76(H76)
2.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C), C77(H77A,H77B,
 H77C)
;
_shelx_res_checksum              45797
_shelx_hkl_checksum              44606
_olex2_submission_special_instructions 'No special instructions were received'