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_1577108
_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         'C10 H28 Cl4 P4 Pt2 Si, C6 H6'
_chemical_formula_sum            'C16 H34 Cl4 P4 Pt2 Si'
_chemical_formula_weight         910.38
_chemical_properties_physical
'Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive,decompose in vacuum'
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-10-28
_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                 94.3660(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.58710(10)
_cell_length_b                   29.4441(2)
_cell_length_c                   9.73830(10)
_cell_measurement_reflns_used    35877
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.7850
_cell_measurement_theta_min      2.9910
_cell_volume                     2740.98(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.100a (Rigaku OD, 2023)'
_computing_data_collection
;
 CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))
;
_computing_data_reduction        'CrysAlisPro 1.171.43.100a (Rigaku OD, 2023)'
_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 2014/5 (Sheldrick, 2014)''
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
 
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w     58.00  88.00   0.50    0.60    --   42.00  52.00 172.66   60
  2  \w     54.00  84.00   0.50    0.60    --   38.00  52.00 178.90   60
  3  \w     54.00  85.00   0.50    0.60    --   38.00  51.00 168.81   62
  4  \w     62.00  92.00   0.50    0.60    --   46.00  52.00 142.52   60
  5  \w     50.00  81.00   0.50    0.60    --   34.00  51.00  -4.70   62
  6  \w     66.00  96.00   0.50    0.60    --   50.00  52.00-168.20   60
  7  \w     58.00  88.00   0.50    0.60    --   42.00  52.00-173.38   60
  8  \w     92.00 118.00   0.50    0.60    --   73.62  15.00-150.00   52
  9  \w     47.00  88.00   0.50    0.60    --   73.62  15.00-150.00   82
 10  \w     60.00  94.00   0.50    0.60    --   83.27  15.00 -90.00   68
 11  \w    103.00 131.00   0.50    0.60    --   83.27  15.00 -90.00   56
 12  \w     89.00 131.00   0.50    0.60    --   83.27  15.00 150.00   84
 13  \w     20.00  66.00   0.50    0.60    --   60.24 -95.00 -60.00   92
 14  \w     33.00  78.00   0.50    0.60    --   73.62 -95.00 -90.00   90
 15  \w     41.00  73.00   0.50    0.60    --   83.27-125.00-150.00   64
 16  \w     45.00  88.00   0.50    0.60    --   83.27 -95.00-150.00   86
 17  \w     49.00  86.00   0.50    0.60    --   83.27 -95.00  30.00   74
 18  \w    -86.00 -41.00   0.50    0.60    --  -79.13 116.00  31.27   90
 19  \w    -96.00 -27.00   0.50    0.60    --  -72.04 125.00 120.00  138
 20  \w    -85.00 -17.00   0.50    0.60    --  -61.82 125.00  30.00  136
 21  \w    -68.00 -34.00   0.50    0.60    --  -75.84 125.00   0.00   68
 22  \w    -85.00 -17.00   0.50    0.60    --  -61.82 125.00 -60.00  136
 23  \w    -93.00 -67.00   0.50    0.60    --  -75.84 125.00 -60.00   52
 24  \w    -58.00 -32.00   0.50    0.60    --  -75.84 125.00 -60.00   52
 25  \w    -66.00 -31.00   0.50    0.60    --  -75.84 125.00 -90.00   70
 26  \w    -99.00 -72.00   0.50    0.60    --  -75.84 125.00 -90.00   54
 27  \w    -71.00 -37.00   0.50    0.60    --  -75.84 125.00-180.00   68
 28  \w    -95.00 -32.00   0.50    0.60    --  -75.84 125.00  90.00  126
 29  \w    -54.00 -28.00   0.50    0.60    --  -14.00 -59.00 161.97   52
 30  \w    -68.00 -37.00   0.50    0.60    --  -22.00 -52.00 129.13   62
 31  \w    -88.00 -57.00   0.50    0.60    --  -42.00 -52.00  97.73   62
 32  \w   -115.00 -88.00   0.50    0.60    --  -74.00 -60.00 173.89   54
 33  \w   -120.00 -94.00   0.50    0.60    --  -79.13 -64.00 174.06   52
 34  \w   -114.00 -85.00   0.50    0.60    --  -70.00 -59.00 155.31   58
 35  \w   -115.00 -89.00   0.50    0.60    --  -74.00 -60.00 146.92   52
 36  \w   -115.00 -89.00   0.50    0.60    --  -74.00 -59.00 123.17   52
 37  \w   -119.00 -93.00   0.50    0.60    --  -79.13 -59.00 112.38   52
 38  \w   -115.00 -85.00   0.50    0.60    --  -70.00 -58.00 165.95   60
 39  \w   -113.00 -88.00   0.50    0.60    --  -74.00 -59.00 115.07   50
 40  \w   -119.00 -93.00   0.50    0.60    --  -79.13 -63.00  57.35   52
 41  \w   -118.00 -93.00   0.50    0.60    --  -74.00 -60.00  28.79   50
 42  \w   -114.00 -88.00   0.50    0.60    --  -74.00 -58.00 130.58   52
 43  \w   -115.00 -89.00   0.50    0.60    --  -74.00 -57.00 138.42   52
 44  \w   -115.00 -84.00   0.50    0.60    --  -70.00 -57.00  95.69   62
 45  \w   -115.00 -84.00   0.50    0.60    --  -70.00 -57.00 122.47   62
 46  \w   -114.00 -89.00   0.50    0.60    --  -74.00 -55.00 130.81   50
 47  \w   -116.00 -90.00   0.50    0.60    --  -74.00 -57.00  36.88   52
 48  \w   -117.00 -89.00   0.50    0.60    --  -74.00 -53.00 -89.41   56
 49  \w   -118.00 -92.00   0.50    0.60    --  -79.13 -62.00-170.85   52
 50  \w   -115.00 -89.00   0.50    0.60    --  -74.00 -58.00-173.79   52
 51  \w   -115.00 -85.00   0.50    0.60    --  -70.00 -58.00-167.83   60
 52  \w   -111.00 -83.00   0.50    0.60    --  -66.00 -55.00-158.95   56
 53  \w   -123.00 -94.00   0.50    0.60    --  -79.13 -52.00 -46.94   58
 54  \w   -108.00 -78.00   0.50    0.60    --  -62.00 -51.00 -70.09   60
 55  \w   -100.00 -70.00   0.50    0.60    --  -54.00 -51.00  88.10   60
 56  \w   -121.00 -94.00   0.50    0.60    --  -79.13 -52.00 144.88   54
 57  \w   -112.00 -82.00   0.50    0.60    --  -66.00 -51.00 162.15   60
 58  \w   -113.00 -82.00   0.50    0.60    --  -66.00 -50.00 135.50   62
 59  \w   -104.00 -73.00   0.50    0.60    --  -58.00 -52.00 134.62   62
 60  \w   -105.00 -74.00   0.50    0.60    --  -58.00 -49.00 155.27   62
 61  \w   -121.00 -95.00   0.50    0.60    --  -79.13 -51.00  85.11   52
 62  \w   -109.00 -78.00   0.50    0.60    --  -62.00 -48.00 117.06   62
 63  \w   -108.00 -78.00   0.50    0.60    --  -62.00 -51.00 110.60   60
 64  \w   -113.00 -82.00   0.50    0.60    --  -66.00 -50.00 102.62   62
 65  \w   -105.00 -74.00   0.50    0.60    --  -58.00 -50.00  81.32   62
 66  \w   -113.00 -82.00   0.50    0.60    --  -66.00 -47.00   2.55   62
 67  \w   -118.00 -85.00   0.50    0.60    --  -70.00 -42.00 -47.19   66
 68  \w   -125.00-100.00   0.50    0.60    --  -79.13 -36.00 -90.35   50
 69  \w   -124.00 -95.00   0.50    0.60    --  -79.13 -37.00-116.55   58
 70  \w   -111.00 -76.00   0.50    0.60    --  -62.00 -39.00 -37.32   70
 71  \w   -119.00 -88.00   0.50    0.60    --  -74.00 -36.00  60.45   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
;
 CrysAlisPro convention (1999,Acta A55,543-557)
;
_diffrn_orient_matrix_UB_11      0.0831341000
_diffrn_orient_matrix_UB_12      -0.0249677000
_diffrn_orient_matrix_UB_13      -0.1062204000
_diffrn_orient_matrix_UB_21      -0.1105491000
_diffrn_orient_matrix_UB_22      0.0138966000
_diffrn_orient_matrix_UB_23      -0.1154255000
_diffrn_orient_matrix_UB_31      0.0823123000
_diffrn_orient_matrix_UB_32      0.0438956000
_diffrn_orient_matrix_UB_33      -0.0239964000
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            51489
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         3.002
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet-R X-ray Source'
_exptl_absorpt_coefficient_mu    25.058
_exptl_absorpt_correction_T_max  0.599
_exptl_absorpt_correction_T_min  0.089
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.43.100a (Rigaku Oxford Diffraction, 2023) Numerical 
 absorption correction based on gaussian integration over a multifaceted 
 crystal model Empirical absorption correction using spherical harmonics, 
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    2.206
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_preparation
;
 Crystals were grown at room temperature \%C from saturated solution in 
 benzene pentane. 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: benzene/pentane'
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.030
_refine_diff_density_max         1.044
_refine_diff_density_min         -0.707
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         5026
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0188
_refine_ls_R_factor_gt           0.0182
_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^)+(0.0192P)^2^+5.8261P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0437
_refine_ls_wR_factor_ref         0.0440
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4934
_reflns_number_total             5026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00337k2.cif
_cod_data_source_block           MaPa103_MaPa_a
_cod_depositor_comments
'Adding full bibliography for 1577098--1577108.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               1577108
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_min   0.082
_shelx_estimated_absorpt_t_max   0.520
_shelx_res_checksum              74861