EPR Spectroscopic Detection of the Elusive FeV═O Intermediates in Selective Catalytic Oxofunctionalizations of Hydrocarbons Mediated by Biomimetic Ferric Complexes
Lyakin, Oleg Y.; Zima, Alexandra M.; Samsonenko, Denis G.; Bryliakov, Konstantin P.; Talsi, Evgenii P.; ACS Catalysis 5 (2015) 2702–; doi:10.1021/acscatal.5b00169

data_4512852
_publ_section_title
;
 EPR Spectroscopic Detection of the Elusive FeV&#x2550;O Intermediates in
 Selective Catalytic Oxofunctionalizations of Hydrocarbons Mediated by
 Biomimetic Ferric Complexes
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              2702
_journal_paper_doi               10.1021/acscatal.5b00169
_journal_volume                  5
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_structural
'(Fe (O H) (C26 H38 N4 O2))2 (C F3 S O3)4 . (C H3 C N)'
_chemical_formula_sum            'C58 H81 F12 Fe2 N9 O18 S4'
_chemical_formula_weight         1660.25
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.9742(9)
_cell_length_b                   17.1155(8)
_cell_length_c                   50.282(3)
_cell_measurement_reflns_used    9136
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.18
_cell_measurement_theta_min      2.35
_cell_volume                     14608.0(14)
_computing_cell_refinement       'SAINT (Bruker-AXS, 2004)'
_computing_data_collection       'APEX2 (Bruker-AXS, 2004)'
_computing_data_reduction        'SAINT (Bruker-AXS, 2004)'
_computing_molecular_graphics    'SHELXTL (Bruker-AXS, 2004)'
_computing_publication_material  'CIFTAB-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 25
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker Apex Duo'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       66
_diffrn_reflns_limit_l_min       -66
_diffrn_reflns_number            76709
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.085
_diffrn_reflns_theta_min         1.439
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.614
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6865
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker-AXS, 2004)'
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_description       block
_exptl_crystal_F_000             6880
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.120
_refine_diff_density_max         1.488
_refine_diff_density_min         -0.946
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 12128 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.021(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2050
_refine_ls_number_reflns         34508
_refine_ls_number_restraints     640
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0644
_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^)+(0.0804P)^2^+27.7880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1604
_refine_ls_wR_factor_ref         0.1657
_reflns_Friedel_coverage         0.819
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                30017
_reflns_number_total             34508
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            cs5b00169_si_002.cif
_cod_data_source_block           fe_pdp
_cod_depositor_comments          'Adding full bibliography for 4512852.cif.'
_cod_original_cell_volume        14608.0(13)
_cod_database_code               4512852
_shelx_estimated_absorpt_t_min   0.867
_shelx_estimated_absorpt_t_max   0.930