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_7712841
_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 H64 Fe Si9'
_chemical_formula_sum            'C28 H64 Fe Si9'
_chemical_formula_weight         709.45
_chemical_name_systematic        5
_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             2023-03-12
_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                63.840(2)
_cell_angle_beta                 77.549(2)
_cell_angle_gamma                88.306(2)
_cell_formula_units_Z            4
_cell_length_a                   11.9336(7)
_cell_length_b                   18.9321(12)
_cell_length_c                   20.4215(13)
_cell_measurement_reflns_used    9830
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.21
_cell_measurement_theta_min      2.28
_cell_volume                     4032.5(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0519
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            133719
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         1.991
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.659
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7097
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0787 before and 0.0592 after correction.
The Ratio of minimum to maximum transmission is 0.9517.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.752
_refine_diff_density_min         -0.476
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     956
_refine_ls_number_reflns         19977
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0534
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0397P)^2^+4.1936P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16911
_reflns_number_total             19977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01133j2.cif
_cod_data_source_block           p-1_CCDC1
_cod_database_code               7712841
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.937
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All Si(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(C23) = Uanis(C22) = Uanis(C2) = Uanis(C21) = Uanis(C1) =
Uanis(C24)
Uanis(C31) = Uanis(C52) = Uanis(C32) = Uanis(C14) = Uanis(C53) = Uanis(C30)
Uanis(C25) = Uanis(C9) = Uanis(C29) = Uanis(C28) = Uanis(C27) = Uanis(C26) =
Uanis(C5)
Uanis(C37) = Uanis(C38) = Uanis(C39) = Uanis(C35) = Uanis(C36) = Uanis(C16) =
Uanis(C15) = Uanis(C19) = Uanis(C18) = Uanis(C17)
3. Others
 Fixed Sof: Si16(0.93) H16(0.93) Si17(0.93) H17(0.93) Si15(0.93) H15(0.93)
 Si18(0.93) H18(0.93) Si8(0.85) H8(0.85) Si9(0.85) H9(0.85) Si5(0.85) H5(0.85)
 Si7(0.85) H7(0.85) Si6(0.85) H6(0.85) Si2(0.75) H2(0.75) Si3(0.75) H3(0.75)
 Si1(0.75) H1(0.75) Si4(0.75) H4(0.75) Si33(0.5) H33(0.5) Si32(0.5) H32(0.5)
 Si10(0.5) H10(0.5) Si14(0.5) H14(0.5) Si31(0.5) H31(0.5) Si34(0.5) H34(0.5)
 Si13(0.5) H13(0.5) Si11(0.5) H11(0.5) Si12(0.5) H12(0.5) Si30(0.5) H30(0.5)
 C8(0.85) H29A(0.85) H29B(0.85) H29C(0.85) H29D(0.15) H29E(0.15) H29F(0.15)
 C5(0.85) C17(0.93) C18(0.93) C15(0.93) C9(0.85) C19(0.93) H19(0.93)
 C1(0.66667) C16(0.93) C2(0.66667) C7(0.85) C32(0.5) C48(0.66667) H48(0.66667)
 H29G(0.85) H29H(0.85) H29I(0.85) H29J(0.15) H29K(0.15) H29L(0.15) H25A(0.85)
 H25B(0.85) H25C(0.85) H25D(0.15) H25E(0.15) H25F(0.15) H37A(0.93) H37B(0.93)
 H37C(0.93) H37D(0.07) H37E(0.07) H37F(0.07) C6(0.85) H32D(0.5) H32E(0.5)
 H32F(0.5) H32A(0.5) H32B(0.5) H32C(0.5) H25G(0.85) H25H(0.85) H25I(0.85)
 H25J(0.15) H25K(0.15) H25L(0.15) H31A(0.5) H31B(0.5) H31C(0.5) H31D(0.5)
 H31E(0.5) H31F(0.5) C4(0.66667) H36A(0.93) H36B(0.93) H36C(0.93) H36D(0.07)
 H36E(0.07) H36F(0.07) H22D(0.25) H22E(0.25) H22F(0.25) H22A(0.75) H22B(0.75)
 H22C(0.75) C31(0.5) H33D(0.5) H33E(0.5) H33F(0.5) H33A(0.5) H33B(0.5)
 H33C(0.5) C3(0.66667) H23D(0.25) H23E(0.25) H23F(0.25) H23A(0.75) H23B(0.75)
 H23C(0.75) H37G(0.93) H37H(0.93) H37I(0.93) H37J(0.07) H37K(0.07) H37L(0.07)
 H36J(0.07) H36K(0.07) H36L(0.07) H36G(0.93) H36H(0.93) H36I(0.93) Si21(0.25)
 H21(0.25) H28A(0.85) H28B(0.85) H28C(0.85) H28D(0.15) H28E(0.15) H28F(0.15)
 H28G(0.85) H28H(0.85) H28I(0.85) H28J(0.15) H28K(0.15) H28L(0.15) C33(0.5)
 Si23(0.25) H23(0.25) Si22(0.25) H22(0.25) H23G(0.75) H23H(0.75) H23I(0.75)
 H23J(0.25) H23K(0.25) H23L(0.25) H35A(0.93) H35B(0.93) H35C(0.93) H35D(0.07)
 H35E(0.07) H35F(0.07) H21D(0.25) H21E(0.25) H21F(0.25) H21A(0.75) H21B(0.75)
 H21C(0.75) H22J(0.25) H22K(0.25) H22L(0.25) H22G(0.75) H22H(0.75) H22I(0.75)
 H26A(0.85) H26B(0.85) H26C(0.85) H26D(0.15) H26E(0.15) H26F(0.15) H38A(0.93)
 H38B(0.93) H38C(0.93) H38D(0.07) H38E(0.07) H38F(0.07) H27A(0.85) H27B(0.85)
 H27C(0.85) H27D(0.15) H27E(0.15) H27F(0.15) H38G(0.93) H38H(0.93) H38I(0.93)
 H38J(0.07) H38K(0.07) H38L(0.07) H21J(0.25) H21K(0.25) H21L(0.25) H21G(0.75)
 H21H(0.75) H21I(0.75) C30(0.5) H34D(0.5) H34E(0.5) H34F(0.5) H34A(0.5)
 H34B(0.5) H34C(0.5) H24A(0.75) H24B(0.75) H24C(0.75) H24D(0.25) H24E(0.25)
 H24F(0.25) C34(0.5) H35G(0.93) H35H(0.93) H35I(0.93) H35J(0.07) H35K(0.07)
 H35L(0.07) H26G(0.85) H26H(0.85) H26I(0.85) H26J(0.15) H26K(0.15) H26L(0.15)
 H27G(0.85) H27H(0.85) H27I(0.85) H27J(0.15) H27K(0.15) H27L(0.15) H30A(0.5)
 H30B(0.5) H30C(0.5) H30D(0.5) H30E(0.5) H30F(0.5) Si24(0.25) H24(0.25)
 H24G(0.75) H24H(0.75) H24I(0.75) H24J(0.25) H24K(0.25) H24L(0.25) Si29(0.15)
 H29(0.15) Si28(0.15) H28(0.15) Si25(0.15) H25(0.15) Si27(0.15) H27(0.15)
 Si26(0.15) H26(0.15) C40(0.33333) H40(0.33333) C24(0.33333) C21(0.33333)
 C22(0.33333) C23(0.33333) C12(0.5) C13(0.5) C53(0.5) C52(0.5) C14(0.5)
 C121(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C131(0.5) H13A(0.5) H13B(0.5)
 H13C(0.5) C301(0.5) H30G(0.5) H30H(0.5) H30I(0.5) C341(0.5) H34G(0.5)
 H34H(0.5) H34I(0.5) C331(0.5) H33G(0.5) H33H(0.5) H33I(0.5) C111(0.5)
 H11A(0.5) H11B(0.5) H11C(0.5) C311(0.5) H31G(0.5) H31H(0.5) H31I(0.5)
 C101(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C321(0.5) H32G(0.5) H32H(0.5)
 H32I(0.5) C141(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C28(0.15) C29(0.15)
 C25(0.15) C27(0.15) C26(0.15) Si35(0.07) H35(0.07) Si36(0.07) H36(0.07)
 Si37(0.07) H37(0.07) Si38(0.07) H38(0.07) C35(0.07) C38(0.07) C39(0.07)
 H39(0.07) C37(0.07) C36(0.07)
4.a Ternary CH refined with riding coordinates:
 Si16(H16), Si17(H17), Si15(H15), Si18(H18), Si8(H8), Si9(H9), Si5(H5),
 Si7(H7), Si6(H6), Si2(H2), Si3(H3), Si1(H1), Si4(H4), Si33(H33), Si32(H32),
 Si10(H10), Si14(H14), Si31(H31), Si34(H34), Si13(H13), Si11(H11), Si12(H12),
 Si30(H30), Si21(H21), Si23(H23), Si22(H22), Si24(H24), Si29(H29), Si28(H28),
 Si25(H25), Si27(H27), Si26(H26), Si35(H35), Si36(H36), Si37(H37), Si38(H38),
 C39(H39)
4.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C48(H48), C40(H40)
4.c Idealised Me refined with everything fixed:
 C251(H25G,H25H,H25I), C251(H25J,H25K,H25L)
4.d Idealised Me refined as rotating group:
 C290(H29A,H29B,H29C), C290(H29D,H29E,H29F), C291(H29G,H29H,H29I), C291(H29J,
 H29K,H29L), C250(H25A,H25B,H25C), C250(H25D,H25E,H25F), C370(H37A,H37B,H37C),
 C370(H37D,H37E,H37F), C320(H32D,H32E,H32F), C320(H32A,H32B,H32C), C310(H31A,
 H31B,H31C), C310(H31D,H31E,H31F), C360(H36A,H36B,H36C), C360(H36D,H36E,H36F),
 C220(H22D,H22E,H22F), C220(H22A,H22B,H22C), C330(H33D,H33E,H33F), C330(H33A,
 H33B,H33C), C230(H23D,H23E,H23F), C230(H23A,H23B,H23C), C371(H37G,H37H,H37I),
 C371(H37J,H37K,H37L), C361(H36J,H36K,H36L), C361(H36G,H36H,H36I), C280(H28A,
 H28B,H28C), C280(H28D,H28E,H28F), C281(H28G,H28H,H28I), C281(H28J,H28K,H28L),
 C231(H23G,H23H,H23I), C231(H23J,H23K,H23L), C350(H35A,H35B,H35C), C350(H35D,
 H35E,H35F), C210(H21D,H21E,H21F), C210(H21A,H21B,H21C), C221(H22J,H22K,H22L),
 C221(H22G,H22H,H22I), C261(H26A,H26B,H26C), C261(H26D,H26E,H26F), C381(H38A,
 H38B,H38C), C381(H38D,H38E,H38F), C271(H27A,H27B,H27C), C271(H27D,H27E,H27F),
 C380(H38G,H38H,H38I), C380(H38J,H38K,H38L), C211(H21J,H21K,H21L), C211(H21G,
 H21H,H21I), C340(H34D,H34E,H34F), C340(H34A,H34B,H34C), C241(H24A,H24B,H24C),
 C241(H24D,H24E,H24F), C351(H35G,H35H,H35I), C351(H35J,H35K,H35L), C260(H26G,
 H26H,H26I), C260(H26J,H26K,H26L), C270(H27G,H27H,H27I), C270(H27J,H27K,H27L),
 C300(H30A,H30B,H30C), C300(H30D,H30E,H30F), C240(H24G,H24H,H24I), C240(H24J,
 H24K,H24L), C121(H12A,H12B,H12C), C131(H13A,H13B,H13C), C301(H30G,H30H,H30I),
 C341(H34G,H34H,H34I), C331(H33G,H33H,H33I), C111(H11A,H11B,H11C), C311(H31G,
 H31H,H31I), C101(H10A,H10B,H10C), C321(H32G,H32H,H32I), C141(H14A,H14B,H14C)
;
_shelx_res_checksum              58068
_olex2_submission_special_instructions 'No special instructions were received'