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_7134905
_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         'C31 H37 P Si2'
_chemical_formula_sum            'C31 H37 P Si2'
_chemical_formula_weight         496.75
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.222(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6524(8)
_cell_length_b                   14.8278(6)
_cell_length_c                   10.6662(5)
_cell_measurement_reflns_used    9889
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.43
_cell_volume                     2846.5(2)
_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 0.997
_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  0.0325
_diffrn_reflns_av_unetI/netI     0.0414
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14177
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.389
_diffrn_reflns_theta_min         2.263
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.198
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5567
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0934 before and 0.0621 after correction.
The Ratio of minimum to maximum transmission is 0.7468.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.138
_refine_diff_density_max         0.233
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 2348 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.196
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         5562
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.195
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0208P)^2^+4.4416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.1009
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.941
_reflns_Friedel_fraction_max     0.912
_reflns_number_gt                5210
_reflns_number_total             5562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04015a2.cif
_cod_data_source_block           leo090_mje
_cod_depositor_comments
'Adding full bibliography for 7134904--7134908.cif.'
_cod_original_sg_symbol_H-M      Cc
_cod_database_code               7134905
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.956
_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:
 C8(H8), C9(H9), C10(H10), C11(H11), C32(H32), C33(H33), C35(H35), C36(H36),
 C42(H42), C43(H43), C45(H45), C46(H46)
2.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C37(H37A,H37B,
 H37C), C47(H47A,H47B,H47C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C)
;
_shelx_res_checksum              37947
_shelx_hkl_checksum              12999
_olex2_submission_special_instructions 'No special instructions were received'