Metal–Metal vs Metal–Ligand Cooperation in Iron-Mediated Activation and Catalytic Reduction of Nitrous Oxide and Nitrobenzene
Jori, Nadir; Corona, Helena; Soto, Enrique; Fernandez, Israel; Campos, Jesús; Chemical Science  (2026) –; doi:10.1039/D5SC07656K

data_1576781
_publ_section_title
;
 Metal-metal <i>vs.</i> metal-ligand cooperation in iron-mediated
 activation and catalytic reduction of nitrous oxide and nitrobenzene.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              9018
_journal_page_last               9026
_journal_paper_doi               10.1039/d5sc07656k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C20 H39 Fe O P2, C32 H12 B F24'
_chemical_formula_sum            'C52 H50.53 B F24 Fe O P2'
_chemical_formula_weight         1276.05
_chemical_properties_physical    Air-sensitive,Oxygen-sensitive
_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
_audit_creation_date             2025-07-23
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7308)
;
_audit_update_record
;
2025-07-23 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                96.854(5)
_cell_angle_beta                 90.903(5)
_cell_angle_gamma                96.757(4)
_cell_formula_units_Z            2
_cell_length_a                   12.3363(14)
_cell_length_b                   12.7312(15)
_cell_length_c                   18.623(2)
_cell_measurement_reflns_used    9956
_cell_measurement_temperature    193.0
_cell_measurement_theta_max      25.319
_cell_measurement_theta_min      2.204
_cell_volume                     2882.5(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  D8Quest_IIQ
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1307
_diffrn_reflns_av_unetI/netI     0.0789
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            70732
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.386
_diffrn_reflns_theta_min         2.023
_exptl_absorpt_coefficient_mu    0.431
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5018
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1311 before and 0.0917 after correction.
The Ratio of minimum to maximum transmission is 0.6734.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic light red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       plate
_exptl_crystal_F_000             1295
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.672
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     895
_refine_ls_number_reflns         10525
_refine_ls_number_restraints     999
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.2406
_refine_ls_R_factor_gt           0.1689
_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^)+(0.1267P)^2^+29.6951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3717
_refine_ls_wR_factor_ref         0.4259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6185
_reflns_number_total             10525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07656k2.cif
_cod_data_source_block           jcm11724a
_cod_depositor_comments
'Adding full bibliography for 1576777--1576784.cif.'
_cod_original_cell_volume        2882.4(6)
_cod_database_code               1576781
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C11-C12A
 1.54 with sigma of 0.02
 C11-C12
 1.54 with sigma of 0.02
 C51-F22 \\sim C51-F22A \\sim C51-F23 \\sim C51-F23A \\sim C51-F24 \\sim
C51-F24A
 with sigma of 0.02
 P1-C15 \\sim P1-C15A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16
 with sigma of 0.02
 F16A-F17A \\sim F17A-F18A \\sim F18A-F16A
 with sigma of 0.02
 C35-F10 \\sim C35-F10A \\sim C35-F12 \\sim C35-F12A \\sim C35-F11 \\sim
C35-F11A
 with sigma of 0.02
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C44-F17 \\sim C44-F17A \\sim C44-F18 \\sim C44-F18A \\sim C44-F16 \\sim
C44-F16A
 with sigma of 0.02
 F10A-F11A \\sim F11A-F12A \\sim F12A-F10A
 with sigma of 0.02
 F16-F17 \\sim F17-F18 \\sim F18-F16
 with sigma of 0.02
 C43-F13 \\sim C43-F13A
 with sigma of 0.02
 C43-F14 \\sim C43-F14A
 with sigma of 0.02
 F10-F11 \\sim F11-F12 \\sim F12-F10
 with sigma of 0.02
 C35-F10A \\sim C35-F11A \\sim C35-F12A \\sim C35-F10 \\sim C35-F11 \\sim
C35-F12
 with sigma of 0.02
 C43-F15 \\sim C43-F15A
 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F15-F13
 with sigma of 0.02
 F22-F23 \\sim F23-F24 \\sim F24-F22
 with sigma of 0.02
 F22A-F23A \\sim F23A-F24A \\sim F24A-F22A
 with sigma of 0.02
 F13A-F14A \\sim F14A-F15A \\sim F15A-F13A
 with sigma of 0.02
 F4-C27 \\sim F4A-C27
 with sigma of 0.02
 F5-C27 \\sim F5A-C27
 with sigma of 0.02
 F6-C27 \\sim F6A-C27
 with sigma of 0.02
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F4-C23 \\sim F4A-C23
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F5-C23 \\sim F5A-C23
 with sigma of 0.04
 F6-C23 \\sim F6A-C23
 with sigma of 0.04
 C27-F4 \\sim C27-F5 \\sim C27-F6
 with sigma of 0.02
 C27-F4A \\sim C27-F5A \\sim C27-F6A
 with sigma of 0.02
 F4-F5 \\sim F5-F6 \\sim F6-F4
 with sigma of 0.02
 F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.02
 F4-F6A \\sim F6A-F5
 with sigma of 0.02
 F4A-F5 \\sim F4A-F6
 with sigma of 0.02
 F5A-F4 \\sim F5A-F6
 with sigma of 0.02
3. Rigid bond restraints
 C11, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 F16, F17A, F18, F16A, F17, C44, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35, F10, F11A, F12, F10A, F11, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F15, F14A, F13A, F14, F15A, F13, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(1)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(2)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(2)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(3)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(4)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(4)
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(5)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(5)
 Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(6)
 Sof(C15)=Sof(H16A)=Sof(H16B)=FVAR(6)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(7)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(7)
7.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C19(H19A,H19B), C15A(H15C,H15D)
7.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C24(H24), C26(H26), C30(H30), C32(H32), C34(H34), C38(H38),
 C40(H40), C42(H42), C46(H46), C48(H48), C50(H50)
7.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C),
 C20(H20A,H20B,H20C), C12A(H12D,H12E,H12F)
;
_shelx_res_checksum              2360
_shelx_hkl_checksum              1862
_olex2_submission_special_instructions 'No special instructions were received'