Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes
Passargus, Max; Nieuwland, Celine; Arrowsmith, Merle; Bickelhaupt, F. Matthias; Braunschweig, Holger; Chemical Science  (2026) –; doi:10.1039/D6SC00337K

data_1577103
_publ_section_title
;
 Cooperative reactivity of halomethanes and -silanes at an A-frame
 complex: transannular addition <i>versus</i> bridging tetrylenes.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              10547
_journal_page_last               10558
_journal_paper_doi               10.1039/d6sc00337k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety
'C11 H30 Br3 Cl3 P4 Pt2 Si, [0.5 (C5 H12) squeezed]'
_chemical_formula_sum
'C13.5 H35 Br3 Cl3 P4 Pt2 Si a an e ed ez ha lf nt pe sq ue'
_chemical_formula_weight         1085.64
_chemical_properties_physical
'Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive,decompose in vacuum'
_space_group_crystal_system      hexagonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-10-29
_audit_creation_method           'CIF-fill 1.6i (K.Radacki, 2005-25)'
_audit_update_record
;
2025-11-26 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            24
_cell_length_a                   36.1930(9)
_cell_length_b                   36.1930(9)
_cell_length_c                   11.8809(5)
_cell_measurement_reflns_used    8390
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.08
_cell_measurement_theta_min      2.43
_cell_volume                     13478.1(7)
_computing_cell_refinement       'Saint+ ver. 8.40B (Bruker AXS)'
_computing_data_collection       'BIS 6.2.14 / APEX4 ver. 2021.10 (Bruker AXS)'
_computing_data_reduction        'Saint+ ver. 8.40B (Bruker AXS)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)''
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 CPA
_diffrn_detector_area_resol_mean 7.5
_diffrn_detector_type            'Photon II'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8-Quest'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type
;
 Sparks R.A., Computational Crystallography p1-18 (Clarendon Press, 1982)
;
_diffrn_orient_matrix_UB_11      -0.0138667
_diffrn_orient_matrix_UB_12      -0.0174564
_diffrn_orient_matrix_UB_13      -0.0686911
_diffrn_orient_matrix_UB_21      0.0260132
_diffrn_orient_matrix_UB_22      0.0190416
_diffrn_orient_matrix_UB_23      -0.0451291
_diffrn_orient_matrix_UB_31      0.0122022
_diffrn_orient_matrix_UB_32      -0.0187231
_diffrn_orient_matrix_UB_33      0.0181471
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0804
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            34238
_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         27.118
_diffrn_reflns_theta_min         2.251
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Incoatec ImS 2.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    18.476
_exptl_absorpt_correction_T_max  0.1819
_exptl_absorpt_correction_T_min  0.1140
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2016/2 (Bruker AXS)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    3.210
_exptl_crystal_description       block
_exptl_crystal_F_000             8676
_exptl_crystal_preparation
;
 For data collection the crystal was immersed in a film of perfluoropolyether 
 oil, mounted on a polyimide loop and transferred to stream of cold nitrogen 
 (Oxford Cryostream 800).
;
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/Pentane'
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.089
_refine_diff_density_max         1.023
_refine_diff_density_min         -0.866
_refine_diff_density_rms         0.187
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     225
_refine_ls_number_reflns         6624
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0331
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0180P)^2^] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0670
_refine_ls_wR_factor_ref         0.0709
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5405
_reflns_number_total             6624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00337k2.cif
_cod_data_source_block           final_a_sq
_cod_depositor_comments
'Adding full bibliography for 1577098--1577108.cif.'
_cod_original_cell_volume        13478.1(9)
_cod_original_formula_sum
'C13.5 H35 Br3 Cl3 P4 Pt2 Si, [half a pentane squeezed]'
_cod_database_code               1577103
_shelx_shelxl_version_number     2019/2
_exptl_absorpt_special_details
;
 Incident beam scaling, empirical absorption correction using spherical 
 harmonics, and outlier rejection was employed as implemented in SADABS. 
 Additional spherical absorption correction with mu*r value set to 1.32 was 
 applied.
;
_shelx_estimated_absorpt_t_min   0.217
_shelx_estimated_absorpt_t_max   0.372
_shelx_res_checksum              85361
_shelx_fab_checksum              13456