Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis.
Sar, Dinabandhu; Yin, Shuai; Grygus, Jacob; Rentería-Gómez, Ángel; Garcia, Melanie; Gutierrez, Osvaldo; Chemical science 14 (2023) 13007–13013; doi:10.1039/d3sc04549h

data_1570162
_publ_section_title
;
 Expanding the chemical space of enol silyl ethers: catalytic
 dicarbofunctionalization enabled by iron catalysis.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              13007
_journal_page_last               13013
_journal_paper_doi               10.1039/d3sc04549h
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C28 H46 Br2 Fe P2 S'
_chemical_formula_sum            'C28 H46 Br2 Fe P2 S'
_chemical_formula_weight         692.32
_chemical_name_systematic        OGB_DS_230316_V_FeBr2
_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             2023-03-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-06 deposited with the CCDC.	2023-10-19 downloaded from the CCDC.
;
_cell_angle_alpha                89.485(2)
_cell_angle_beta                 71.022(2)
_cell_angle_gamma                89.930(2)
_cell_formula_units_Z            8
_cell_length_a                   17.1165(5)
_cell_length_b                   19.8953(6)
_cell_length_c                   20.7440(7)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      70.049
_cell_measurement_theta_min      2.252
_cell_volume                     6679.9(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'APEX 3 (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker Venture (PHOTON III)'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0601
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            231826
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.316
_diffrn_reflns_theta_min         2.221
_diffrn_source                   'Bruker Venture Cu-IuS'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.009
_exptl_absorpt_correction_T_max  0.3220
_exptl_absorpt_correction_T_min  0.1886
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0972 before and 0.0782 after correction.
The Ratio of minimum to maximum transmission is 0.5857.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       block
_exptl_crystal_F_000             2848
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.642
_refine_diff_density_min         -1.171
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1387
_refine_ls_number_reflns         25346
_refine_ls_number_restraints     932
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0573P)^2^+20.5427P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1231
_refine_ls_wR_factor_ref         0.1266
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22952
_reflns_number_total             25346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04549h2.cif
_cod_data_source_block           og_dsfebr2
_cod_depositor_comments
'Adding full bibliography for 1570159--1570162.cif.'
_cod_database_code               1570162
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.539
_shelx_estimated_absorpt_t_min   0.218
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{C18F, C22G}
3. Restrained distances
 P1D-C11E \\sim P1D-C11D
 with sigma of 0.01
 P2F-C17F \\sim P2F-C17G
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C5B \\sim C6B \\sim C7B \\sim C8B \\sim C9B \\sim C10B \\sim C5C \\sim C6C
\\sim C7C \\sim C8C \\sim C9C \\sim C10C: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C11D \\sim C12D \\sim C13D \\sim C14D \\sim C15D \\sim C16D \\sim C11E \\sim
C12E \\sim C13E \\sim C14E \\sim C15E \\sim C16E: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C17F \\sim C18F \\sim C19F \\sim C20F \\sim C21F \\sim C22F \\sim C17G \\sim
C18G \\sim C19G \\sim C20G \\sim C21G \\sim C22G: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 C5B, C6B, C7B, C8B, C9B, C10B, C5C, C6C, C7C, C8C, C9C, C10C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11D, C12D, C13D, C14D, C15D, C16D, C11E, C12E, C13E, C14E, C15E, C16E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17F, C18F, C19F, C20F, C21F, C22F, C17G, C18G, C19G, C20G, C21G, C22G
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Same fragment restrains
{C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C11D, C12D, C13D, C14D, C15D, C16D}
{C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C5C, C6C, C7C, C8C, C9C, C10C}
{C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C11E, C12E, C13E, C14E, C15E, C16E}
{C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C17F, C18F, C19F, C20F, C21F, C22F}
{C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C17G, C18G, C19G, C20G, C21G, C22G}
7. Others
 Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(H6CA)=Sof(H6CB)=Sof(C7C)=Sof(H7CA)=Sof(H7CB)=
 Sof(C8C)=Sof(H8CA)=Sof(H8CB)=Sof(C9C)=Sof(H9CA)=Sof(H9CB)=Sof(C10C)=Sof(H10C)=
 Sof(H10D)=1-FVAR(1)
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6BA)=Sof(H6BB)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=
 Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C10B)=Sof(H10A)=
 Sof(H10B)=FVAR(1)
 Sof(C11E)=Sof(H11E)=Sof(C12E)=Sof(H12E)=Sof(H12F)=Sof(C13E)=Sof(H13E)=
 Sof(H13F)=Sof(C14E)=Sof(H14E)=Sof(H14F)=Sof(C15E)=Sof(H15E)=Sof(H15F)=
 Sof(C16E)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(C11D)=Sof(H11D)=Sof(C12D)=Sof(H12C)=Sof(H12D)=Sof(C13D)=Sof(H13C)=
 Sof(H13D)=Sof(C14D)=Sof(H14C)=Sof(H14D)=Sof(C15D)=Sof(H15C)=Sof(H15D)=
 Sof(C16D)=Sof(H16C)=Sof(H16D)=FVAR(2)
 Sof(C17G)=Sof(H17G)=Sof(C18G)=Sof(H18G)=Sof(H18H)=Sof(C19G)=Sof(H19G)=
 Sof(H19H)=Sof(C20G)=Sof(H20G)=Sof(H20H)=Sof(C21G)=Sof(H21G)=Sof(H21H)=
 Sof(C22G)=Sof(H22G)=Sof(H22H)=1-FVAR(3)
 Sof(C17F)=Sof(H17F)=Sof(C18F)=Sof(H18E)=Sof(H18F)=Sof(C19F)=Sof(H19E)=
 Sof(H19F)=Sof(C20F)=Sof(H20E)=Sof(H20F)=Sof(C21F)=Sof(H21E)=Sof(H21F)=
 Sof(C22F)=Sof(H22E)=Sof(H22F)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C5(H5), C5D(H5D), C5F(H5F), C11(H11), C11B(H11B), C11F(H11F), C17(H17),
 C17B(H17B), C17D(H17D), C23(H23), C23B(H23B), C23D(H23D), C23F(H23F), C5B(H5B),
  C11D(H11D), C17F(H17F), C5C(H5C), C11E(H11E), C17G(H17G)
8.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10I,H10J), C6D(H6DA,
 H6DB), C6F(H6FA,H6FB), C7D(H7DA,H7DB), C7F(H7FA,H7FB), C8D(H8DA,H8DB),
 C8F(H8FA,H8FB), C9D(H9DA,H9DB), C9F(H9FA,H9FB), C10D(H10E,H10F), C10F(H10G,
 H10H), C12(H12I,H12J), C12B(H12A,H12B), C12F(H12G,H12H), C13(H13I,H13J),
 C13B(H13A,H13B), C13F(H13G,H13H), C14(H14I,H14J), C14B(H14A,H14B), C14F(H14G,
 H14H), C15(H15I,H15J), C15B(H15A,H15B), C15F(H15G,H15H), C16(H16I,H16J),
 C16B(H16A,H16B), C16F(H16G,H16H), C18(H18I,H18J), C18B(H18A,H18B), C18D(H18C,
 H18D), C19(H19I,H19J), C19B(H19A,H19B), C19D(H19C,H19D), C20(H20I,H20J),
 C20B(H20A,H20B), C20D(H20C,H20D), C21(H21I,H21J), C21B(H21A,H21B), C21D(H21C,
 H21D), C22(H22I,H22J), C22B(H22A,H22B), C22D(H22C,H22D), C24(H24G,H24H),
 C24B(H24A,H24B), C24D(H24C,H24D), C24F(H24E,H24F), C25(H25G,H25H), C25B(H25A,
 H25B), C25D(H25C,H25D), C25F(H25E,H25F), C26(H26G,H26H), C26B(H26A,H26B),
 C26D(H26C,H26D), C26F(H26E,H26F), C27(H27G,H27H), C27B(H27A,H27B), C27D(H27C,
 H27D), C27F(H27E,H27F), C28(H28G,H28H), C28B(H28A,H28B), C28D(H28C,H28D),
 C28F(H28E,H28F), C6B(H6BA,H6BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,
 H9BB), C10B(H10A,H10B), C12D(H12C,H12D), C13D(H13C,H13D), C14D(H14C,H14D),
 C15D(H15C,H15D), C16D(H16C,H16D), C18F(H18E,H18F), C19F(H19E,H19F), C20F(H20E,
 H20F), C21F(H21E,H21F), C22F(H22E,H22F), C6C(H6CA,H6CB), C7C(H7CA,H7CB),
 C8C(H8CA,H8CB), C9C(H9CA,H9CB), C10C(H10C,H10D), C12E(H12E,H12F), C13E(H13E,
 H13F), C14E(H14E,H14F), C15E(H15E,H15F), C16E(H16E,H16F), C18G(H18G,H18H),
 C19G(H19G,H19H), C20G(H20G,H20H), C21G(H21G,H21H), C22G(H22G,H22H)
8.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C1B(H1B), C1D(H1D), C1F(H1F), C4(H4), C4B(H4B), C4D(H4D), C4F(H4F)
;
_smtbx_masks_special_details
;
THF was used as solvent. Two positions were found 
for the solvent molecules. Our trials suggested the 
solvent molecules were partially occupied and were 
disordered. For the final least squares refinement 
cycles, the solvent molecules were MASKed using 
OLEX2. The electron count suggested presence of, on average, 
0.41 molecules of THF per molecule of FeBr2 complex. 
A solvent mask was calculated and 131 electrons were 
found in a volume of 681\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.41[C4H8O] per Asymmetric Unit 
which account for 132 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              29727
_shelx_fab_checksum              26753
_olex2_submission_original_sample_id OGB_DS_230316_V_FeBr2
_olex2_submission_special_instructions 'No special instructions were received'