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_1576783
_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         'C26 H44 Fe N O P2, C32 H12 B F24, C4 H10 O'
_chemical_formula_sum            'C62 H66 B F24 Fe N O2 P2'
_chemical_formula_weight         1441.75
_chemical_name_systematic        C62H66BF24FeNO2P2
_chemical_properties_physical    Air-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-18
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-23 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 123.835(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   42.290(5)
_cell_length_b                   14.2781(17)
_cell_length_c                   25.930(3)
_cell_measurement_reflns_used    8818
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      25.058
_cell_measurement_theta_min      2.230
_cell_volume                     13005(3)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1681
_diffrn_reflns_av_unetI/netI     0.0718
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            108796
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.121
_diffrn_reflns_theta_max         25.121
_diffrn_reflns_theta_min         1.968
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.393
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5971
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1228 before and 0.0671 after correction.
The Ratio of minimum to maximum transmission is 0.8013.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic light yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       plate
_exptl_crystal_F_000             5904
_exptl_crystal_preparation       'toluene -30degrees'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.722
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     953
_refine_ls_number_reflns         11544
_refine_ls_number_restraints     285
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1436
_refine_ls_R_factor_gt           0.0928
_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^)+(0.0879P)^2^+101.3521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2136
_refine_ls_wR_factor_ref         0.2445
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7342
_reflns_number_total             11544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07656k2.cif
_cod_data_source_block           jcm22924a
_cod_depositor_comments
'Adding full bibliography for 1576777--1576784.cif.'
_cod_original_cell_volume        13006(3)
_cod_database_code               1576783
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.926
_olex2_refinement_description
;
1. Restrained distances
 P2-C19A \\sim P2-C19
 with sigma of 0.02
 F18-C50 \\sim F18A-C50
 with sigma of 0.02
 C50-F16 \\sim C50-F16A
 with sigma of 0.02
 C50-F17 \\sim C50-F17A
 with sigma of 0.02
 F18-C47 \\sim F18A-C47
 with sigma of 0.04
 F18-F16 \\sim F18A-F16A
 with sigma of 0.04
 F18-F17 \\sim F18A-F17A
 with sigma of 0.04
 C47-F16 \\sim C47-F16A
 with sigma of 0.04
 C47-F17 \\sim C47-F17A
 with sigma of 0.04
 F16-F17 \\sim F16A-F17A
 with sigma of 0.04
 C20A-C19A \\sim C20-C19
 with sigma of 0.02
 P2-C20A \\sim P2-C20
 with sigma of 0.04
 F23-C33 \\sim F22A-C33
 with sigma of 0.02
 F24-C33 \\sim F23A-C33
 with sigma of 0.02
 F13-C49 \\sim F13A-C49
 with sigma of 0.02
 C49-F14 \\sim C49-F14A
 with sigma of 0.02
 F22-C33 \\sim F24A-C33
 with sigma of 0.02
 C29-F23 \\sim C29-F22A
 with sigma of 0.04
 C49-F15 \\sim C49-F15A
 with sigma of 0.02
 C29-F24 \\sim C29-F23A
 with sigma of 0.04
 F13-C45 \\sim F13A-C45
 with sigma of 0.04
 C29-F22 \\sim C29-F24A
 with sigma of 0.04
 F13-F14 \\sim F13A-F14A
 with sigma of 0.04
 F13-F15 \\sim F13A-F15A
 with sigma of 0.04
 F23-F24 \\sim F22A-F23A
 with sigma of 0.04
 F23-F22 \\sim F22A-F24A
 with sigma of 0.04
 C45-F14 \\sim C45-F14A
 with sigma of 0.04
 F24-F22 \\sim F23A-F24A
 with sigma of 0.04
 C45-F15 \\sim C45-F15A
 with sigma of 0.04
 F14-F15 \\sim F14A-F15A
 with sigma of 0.04
 P1-C15 \\sim P2-C16
 with sigma of 0.02
 C21-C22 \\sim C22-C23 \\sim C23-C24 \\sim C24-C25 \\sim C25-C26 \\sim C26-C21
 with sigma of 0.02
2. Rigid bond restraints
 C50, F18, F17, F16
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C50, F18A, F17A, F16A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C49, F15, F13, F14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C49, F15A, F13A, F14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C33, F22, F23, F24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C33, F23A, F22A, F24A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C26, C25, C24, C23, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C50 \\sim F18 \\sim F17 \\sim F16: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C50 \\sim F18A \\sim F17A \\sim F16A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.7A
C49 \\sim F15 \\sim F13 \\sim F14: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C49 \\sim F15A \\sim F13A \\sim F14A: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C21 \\sim C26 \\sim C25 \\sim C24 \\sim C23 \\sim C22: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
4. Rigid body (RIGU) restrains
 C50, F18, F17, F16, F18A, F17A, F16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C26, C25, C24, C23, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1, C15, C16, P2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C19)=Sof(H19C)=Sof(H19D)=Sof(C20)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C19A)=Sof(H19A)=Sof(H19B)=FVAR(1)
 Sof(F22A)=Sof(F24A)=Sof(F23A)=1-FVAR(2)
 Sof(F23)=Sof(F24)=Sof(F22)=FVAR(2)
 Sof(F13A)=Sof(F15A)=Sof(F14A)=1-FVAR(3)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(4)
 Sof(F18)=Sof(F16)=Sof(F17)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C17(H17A,H17B), C15(H15A,H15B), C16(H16A,
 H16B), C60(H60A,H60B), C61(H61A,H61B), C19A(H19A,H19B), C19(H19C,H19D)
6.b Aromatic/amide H refined with riding coordinates:
 C28(H28), C40(H40), C44(H44), C32(H32), C52(H52), C56(H56), C38(H38),
 C36(H36), C30(H30), C48(H48), C46(H46), C54(H54), C22(H22), C26(H26), C23(H23),
  C24(H24), C25(H25)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C7(H7A,H7B,H7C),
 C18(H18A,H18B,H18C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C),
  C62(H62A,H62B,H62C), C59(H59A,H59B,H59C), C20A(H20A,H20B,H20C), C20(H20D,H20E,
 H20F)
;
_shelx_res_checksum              62102
_shelx_hkl_checksum              63917
_olex2_submission_special_instructions 'No special instructions were received'