Persilylation of Ferrocene: The Ultimate Discipline in Sterically Overcrowded Metal Complexes
Rupf, Susanne M.; Sievers, Robin; Riemann, Paulin S.; Reimann, Marc; Kaupp, Martin; Fasting, Dr. Carlo; Malischewski, Moritz; Dalton Transactions  (2023) –; doi:10.1039/D3DT01133J

data_7712837
_publ_section_title
;
 Persilylation of Ferrocene: The Ultimate Discipline in Sterically
 Overcrowded Metal Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01133J
_journal_year                    2023
_chemical_formula_moiety         'C28 H63 Br Fe Si9'
_chemical_formula_sum            'C28 H63 Br Fe Si9'
_chemical_formula_weight         788.35
_chemical_name_systematic        2
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-04
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2023-03-12 deposited with the CCDC.	2023-04-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7129(9)
_cell_length_b                   18.7916(7)
_cell_length_c                   12.3172(6)
_cell_measurement_reflns_used    9859
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      28.24
_cell_measurement_theta_min      2.54
_cell_volume                     4099.8(3)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_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  0.0502
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            72426
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.301
_diffrn_reflns_theta_min         2.014
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.624
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0772 before and 0.0584 after correction.
The Ratio of minimum to maximum transmission is 0.9195.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         5235
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0295
_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^)+(0.0403P)^2^+2.8846P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0788
_refine_ls_wR_factor_ref         0.0820
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4622
_reflns_number_total             5235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01133j2.cif
_cod_data_source_block           pnma
_cod_database_code               7712837
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.759
_shelx_estimated_absorpt_t_min   0.716
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All Si(H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups
2. Shared sites
{Si13, Si23}
{Br1, Br2}
3. Uiso/Uaniso restraints and constraints
Uanis(Si13) = Uanis(Si23)
Uanis(Br1) = Uanis(Br2)
4. Others
 Fixed Sof: Br1(0.25) Br2(0.25) Si11(0.5) H11(0.5) Si12(0.5) H12(0.5)
 Si13(0.25) H13(0.25) Si14(0.5) H14(0.5) Si15(0.5) H15(0.5) Si21(0.5) H21(0.5)
 Si22(0.5) H22(0.5) Si23(0.25) H23(0.25) Si24(0.5) H24(0.5) Si25(0.5) H25(0.5)
 H11D(0.5) H11E(0.5) H11F(0.5) H11A(0.5) H11B(0.5) H11C(0.5) H12A(0.5)
 H12B(0.5) H12C(0.5) H12D(0.5) H12E(0.5) H12F(0.5) H13A(0.25) H13B(0.25)
 H13C(0.25) H13D(0.25) H13E(0.25) H13F(0.25) H14A(0.5) H14B(0.5) H14C(0.5)
 H14D(0.5) H14E(0.5) H14F(0.5) H15A(0.5) H15B(0.5) H15C(0.5) H15D(0.5)
 H15E(0.5) H15F(0.5) H21D(0.5) H21E(0.5) H21F(0.5) H21A(0.5) H21B(0.5)
 H21C(0.5) H22A(0.5) H22B(0.5) H22C(0.5) H22D(0.5) H22E(0.5) H22F(0.5)
 H23E(0.25) H23D(0.25) H23F(0.25) H23B(0.25) H23A(0.25) H23C(0.25) H24A(0.5)
 H24B(0.5) H24C(0.5) H24D(0.5) H24E(0.5) H24F(0.5) H25A(0.5) H25B(0.5)
 H25C(0.5) H25D(0.5) H25E(0.5) H25F(0.5)
5.a Ternary CH refined with riding coordinates:
 Si11(H11), Si12(H12), Si13(H13), Si14(H14), Si15(H15), Si21(H21), Si22(H22),
 Si23(H23), Si24(H24), Si25(H25)
5.b Idealised Me refined with everything fixed:
 C13(H13A,H13B,H13C), C13(H13D,H13E,H13F)
5.c Idealised Me refined as rotating group:
 C11(H11D,H11E,H11F), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C12(H12D,H12E,
 H12F), C14(H14A,H14B,H14C), C14(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15(H15D,
 H15E,H15F), C21(H21D,H21E,H21F), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C22(H22D,H22E,H22F), C23(H23E,H23D,H23F), C23(H23B,H23A,H23C), C24(H24A,H24B,
 H24C), C24(H24D,H24E,H24F), C25(H25A,H25B,H25C), C25(H25D,H25E,H25F)
;
_shelx_res_checksum              85874
_olex2_submission_special_instructions 'No special instructions were received'