Mononuclear Fe(I) and Fe(II) Acetylene Adducts and Their Reductive Protonation to Terminal Fe(IV) and Fe(V) Carbynes.
Citek, Cooper; Oyala, Paul H.; Peters, Jonas C.; Journal of the American Chemical Society 141 (2019) 15211–15221; doi:10.1021/jacs.9b06987

data_4128993
_publ_section_title
;
 Mononuclear Fe(I) and Fe(II) Acetylene Adducts and Their Reductive
 Protonation to Terminal Fe(IV) and Fe(V) Carbynes.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15211
_journal_page_last               15221
_journal_paper_doi               10.1021/jacs.9b06987
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C38 H57 Fe P3 Si, C F3 O3 S'
_chemical_formula_sum            'C39 H57 F3 Fe O3 P3 S Si'
_chemical_formula_weight         839.75
_chemical_name_systematic        SiP3FeCCH3OTf
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.173(5)
_cell_length_b                   15.284(6)
_cell_length_c                   20.312(7)
_cell_measurement_reflns_used    4056
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.9
_cell_measurement_theta_min      2.5
_cell_volume                     4090(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.925
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0670
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.925
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            90778
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.979
_diffrn_reflns_theta_min         2.665
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.616
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8646
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0851 before and 0.0605 after correction.
The Ratio of minimum to maximum transmission is 0.8646.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_description       blob
_exptl_crystal_F_000             1772
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.482
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.457(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     559
_refine_ls_number_reflns         16037
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0733
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0415P)^2^+1.3202P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0881
_refine_ls_wR_factor_ref         0.0987
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.854
_reflns_number_gt                12475
_reflns_number_total             16037
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06987_si_002.cif
_cod_data_source_block           p17558
_cod_database_code               4128993
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.851
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.543(14)
 0.457(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S2-O3 \\sim S1-O2
 with sigma of 0.02
 S1-O4 \\sim S2-O1
 with sigma of 0.02
 F2-C41 \\sim F3-C42
 with sigma of 0.02
 F1-C42 \\sim F4-C41
 with sigma of 0.02
 S2-C42 \\sim S1-C41
 with sigma of 0.02
4. Others
 Sof(C30)=Sof(H30)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(H35C)=1-FVAR(1)
 Sof(C31)=Sof(H31)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(H34C)=FVAR(1)
 Sof(S1)=Sof(F2)=Sof(F4)=Sof(O2)=Sof(O4)=Sof(C41)=1-FVAR(2)
 Sof(S2)=Sof(F1)=Sof(F3)=Sof(O1)=Sof(O3)=Sof(C42)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C5(H5), C15(H15), C18(H18), C27(H27), C31(H31), C30(H30)
5.b Aromatic/amide H refined with riding coordinates:
 C43(H43), C11(H11), C12(H12), C13(H13), C14(H14), C22(H22), C23(H23),
 C24(H24), C25(H25), C38(H38), C39(H39), C40(H40)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,
 H8B,H8C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C),
 C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C32(H32A,H32B,H32C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              40954
_shelx_hkl_checksum              16621
_olex2_submission_original_sample_id SiP3FeCCH3OTf
_olex2_submission_special_instructions 'No special instructions were received'