On-demand switching from mono-silylene to bis-silylene to access mono-, di- and mixed coinage metal complexes.
Sun, Xiaofei; Jin, Da; Yadav, Ravi; Kraetschmer, Frederic; Köppe, Ralf; Roesky, Peter W.; Chemical science 16 (2025) 16057–16062; doi:10.1039/d5sc04287a

data_1575465
_publ_section_title
;
 On-demand switching from mono-silylene to bis-silylene to access mono-,
 di- and mixed coinage metal complexes.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              16057
_journal_page_last               16062
_journal_paper_doi               10.1039/d5sc04287a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C51 H74 Au N5 Si2, 1.5(C6 D6)'
_chemical_formula_sum            'C60 H74 Au D9 N5 Si2'
_chemical_formula_weight         1136.51
_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             2024-01-25
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                71.514(6)
_cell_angle_beta                 69.239(10)
_cell_angle_gamma                70.868(10)
_cell_formula_units_Z            2
_cell_length_a                   12.4819(19)
_cell_length_b                   15.9578(12)
_cell_length_c                   16.7970(14)
_cell_measurement_reflns_used    51197
_cell_measurement_temperature    110
_cell_measurement_theta_max      31.15
_cell_measurement_theta_min      1.39
_cell_volume                     2878.2(6)
_computing_cell_refinement       'X-Area Recipe 1.37.0.0 (STOE, 2021)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)'
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area X-Red 2.3.0.0 (STOE, 2021)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      110
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
 537 frames, detector distance = 40 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0350
_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       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28043
_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         25.999
_diffrn_reflns_theta_min         1.799
_diffrn_source                   'Mo Genix 3D HF'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.638
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.2993
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1170
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.094
_refine_diff_density_min         -0.760
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     691
_refine_ls_number_reflns         11285
_refine_ls_number_restraints     229
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0294
_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^)+(0.0464P)^2^+0.8976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0713
_refine_ls_wR_factor_ref         0.0736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10182
_reflns_number_total             11285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04287a2.cif
_cod_data_source_block           xf518a
_cod_depositor_comments
'Adding full bibliography for 1575461--1575467.cif.'
_cod_database_code               1575465
__shelx_shelxl_version_number    2019/2
_audit_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_audit_contact_letter
;
;
_shelx_estimated_absorpt_t_max   0.693
_shelx_estimated_absorpt_t_min   0.500
_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. Restrained distances
 C53-C52 \\sim C53A-C52A
 with sigma of 0.02
 C59-C58 \\sim C60-C59
 with sigma of 0.02
 C56-C54 \\sim C56A-C54A
 with sigma of 0.04
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C52-C57 \\sim C52A-C57A
 with sigma of 0.02
 C57-C56 \\sim C57A-C56A
 with sigma of 0.02
 C56-C55 \\sim C56A-C55A
 with sigma of 0.02
 C55-C54 \\sim C55A-C54A
 with sigma of 0.02
 C57-C55 \\sim C57A-C55A
 with sigma of 0.04
 C53-C57 \\sim C53A-C57A
 with sigma of 0.04
 C53-C55 \\sim C53A-C55A
 with sigma of 0.04
 C52-C56 \\sim C52A-C56A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C52 \\sim C52A \\sim C53A \\sim C54 \\sim C54A \\sim C55 \\sim C55A \\sim C56
\\sim C56A \\sim C57 \\sim C57A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C53A)=Sof(D53A)=Sof(C52A)=Sof(D52A)=Sof(C57A)=Sof(D57A)=Sof(C56A)=
 Sof(D56A)=Sof(C55A)=Sof(D55A)=Sof(C54A)=Sof(D54A)=1-FVAR(1)
 Sof(C53)=Sof(D53)=Sof(C52)=Sof(D52)=Sof(C57)=Sof(D57)=Sof(C56)=Sof(D56)=
 Sof(C55)=Sof(D55)=Sof(C54)=Sof(D54)=FVAR(1)
 Sof(C61)=Sof(D61)=Sof(C62)=Sof(D62)=Sof(C63)=Sof(D63)=1-FVAR(2)
 Sof(C58)=Sof(D58)=Sof(C59)=Sof(D59)=Sof(C60)=Sof(D60)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C12(H12), C13(H13), C14(H14), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C53(D53),
  C52(D52), C57(D57), C56(D56), C55(D55), C54(D54), C53A(D53A), C52A(D52A),
 C57A(D57A), C56A(D56A), C55A(D55A), C54A(D54A), C58(D58), C59(D59), C60(D60),
 C61(D61), C62(D62), C63(D63)
5.c Fitted hexagon refined as free rotating group:
 C53(C52,C57,C56,C55,C54), C53A(C52A,C57A,C56A,C55A,C54A)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C)
;
_shelx_res_checksum              55472
_olex2_submission_special_instructions 'No special instructions were received'