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_1576780
_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 P2, C32 H12 B F24'
_chemical_formula_sum            'C52 H51 B F24 Fe P2'
_chemical_formula_weight         1260.52
_chemical_name_systematic        C52H51BF24FeP2
_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             2025-07-21
_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                91.121(2)
_cell_angle_beta                 95.599(2)
_cell_angle_gamma                94.996(2)
_cell_formula_units_Z            4
_cell_length_a                   12.2745(5)
_cell_length_b                   12.7920(6)
_cell_length_c                   36.6240(15)
_cell_measurement_reflns_used    9702
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      26.24
_cell_measurement_theta_min      2.25
_cell_volume                     5699.1(4)
_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)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0441
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            66992
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.501
_diffrn_reflns_theta_min         1.918
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.434
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6182
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1275 before and 0.0506 after correction.
The Ratio of minimum to maximum transmission is 0.8294.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic light orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       plate
_exptl_crystal_F_000             2560
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.154
_refine_diff_density_min         -1.256
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1668
_refine_ls_number_reflns         23426
_refine_ls_number_restraints     798
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1395
_refine_ls_R_factor_gt           0.1067
_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^)+(0.1744P)^2^+15.9473P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2948
_refine_ls_wR_factor_ref         0.3231
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16186
_reflns_number_total             23426
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07656k2.cif
_cod_data_source_block           jcm19124a_a
_cod_depositor_comments
'Adding full bibliography for 1576777--1576784.cif.'
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               1576780
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.918
_olex2_refinement_description
;
1. Restrained distances
 C53-C54
 1.52 with sigma of 0.005
 C55-C56
 1.5 with sigma of 0.01
 P1-C13 \\sim P1-C11 \\sim P2-C17 \\sim P2-C19
 with sigma of 0.02
 P3-C53 \\sim P3-C55 \\sim P4-C59 \\sim P4-C61
 with sigma of 0.01
 C95-F40 \\sim C95-F41 \\sim C95-F42
 with sigma of 0.01
 C95-F40A \\sim C95-F41A \\sim C95-F42A
 with sigma of 0.01
 C28-F16 \\sim C28-F17 \\sim C28-F18
 with sigma of 0.02
 C28-F16A \\sim C28-F17A \\sim C28-F18A
 with sigma of 0.02
 F40-F41 \\sim F41-F42 \\sim F42-F40
 with sigma of 0.01
 F37-C87 \\sim F37A-C87
 with sigma of 0.02
 F40A-F41A \\sim F41A-F42A \\sim F42A-F40A
 with sigma of 0.01
 C87-F38 \\sim C87-F38A
 with sigma of 0.02
 C87-F39 \\sim C87-F39A
 with sigma of 0.02
 C83-F37 \\sim C83-F37A
 with sigma of 0.04
 C83-F38 \\sim C83-F38A
 with sigma of 0.04
 C83-F39 \\sim C83-F39A
 with sigma of 0.04
 F37-F38 \\sim F37A-F38A
 with sigma of 0.04
 F37-F39 \\sim F37A-F39A
 with sigma of 0.04
 F38-F39 \\sim F38A-F39A
 with sigma of 0.04
 C87-F38 \\sim C87-F39 \\sim C87-F37
 with sigma of 0.02
 C87-F38A \\sim C87-F39A \\sim C87-F37A
 with sigma of 0.02
 F37-F38 \\sim F38-F39 \\sim F39-F37
 with sigma of 0.02
 F37A-F38A \\sim F38A-F39A \\sim F39A-F37A
 with sigma of 0.02
 F30-C79 \\sim F30A-C79
 with sigma of 0.02
 C25-F16 \\sim C25-F16A
 with sigma of 0.04
 F29-C79 \\sim F29A-C79
 with sigma of 0.02
 F28-C79 \\sim F28A-C79
 with sigma of 0.02
 C75-F30 \\sim C75-F30A
 with sigma of 0.04
 C75-F29 \\sim C75-F29A
 with sigma of 0.04
 C75-F28 \\sim C75-F28A
 with sigma of 0.04
 F30-F29 \\sim F30A-F29A
 with sigma of 0.04
 F30-F28 \\sim F30A-F28A
 with sigma of 0.04
 F29-F28 \\sim F29A-F28A
 with sigma of 0.04
 C79-F28 \\sim C79-F29 \\sim C79-F30
 with sigma of 0.02
 C63-C64 \\sim C64-C65 \\sim C65-C66 \\sim C66-C67 \\sim C67-C63
 with sigma of 0.02
 P1-C15 \\sim P2-C16
 with sigma of 0.02
 C79-F28A \\sim C79-F29A \\sim C79-F30A
 with sigma of 0.02
 C63-C68 \\sim C64-C69 \\sim C65-C70 \\sim C66-C71 \\sim C67-C72
 with sigma of 0.02
 F28-F29 \\sim F29-F30 \\sim F30-F28
 with sigma of 0.02
 P3-C57 \\sim P4-C58
 with sigma of 0.02
 F28A-F29A \\sim F29A-F30A \\sim F30A-F28A
 with sigma of 0.02
 F25-C80 \\sim F25A-C80
 with sigma of 0.02
 F27-C80 \\sim F27A-C80
 with sigma of 0.02
 C80-F26 \\sim C80-F26A
 with sigma of 0.02
 F25-C77 \\sim F25A-C77
 with sigma of 0.04
 F25-F27 \\sim F25A-F27A
 with sigma of 0.04
 F25-F26 \\sim F25A-F26A
 with sigma of 0.04
 C77-F27 \\sim C77-F27A
 with sigma of 0.04
 C77-F26 \\sim C77-F26A
 with sigma of 0.04
 F27-F26 \\sim F27A-F26A
 with sigma of 0.04
 C80-F25 \\sim C80-F26 \\sim C80-F27
 with sigma of 0.02
 C80-F25A \\sim C80-F26A \\sim C80-F27A
 with sigma of 0.02
 F25-F26 \\sim F26-F27 \\sim F27-F25
 with sigma of 0.02
 F25A-F26A \\sim F26A-F27A \\sim F27A-F25A
 with sigma of 0.02
 F23-C44 \\sim F23A-C44
 with sigma of 0.02
 F24-C44 \\sim F24A-C44
 with sigma of 0.02
 C44-F22 \\sim C44-F22A
 with sigma of 0.02
 C41-F23 \\sim C41-F23A
 with sigma of 0.04
 C41-F24 \\sim C41-F24A
 with sigma of 0.04
 C41-F22 \\sim C41-F22A
 with sigma of 0.04
 F23-F24 \\sim F23A-F24A
 with sigma of 0.04
 F23-F22 \\sim F23A-F22A
 with sigma of 0.04
 F24-F22 \\sim F24A-F22A
 with sigma of 0.04
 C44-F22 \\sim C44-F23 \\sim C44-F24
 with sigma of 0.02
 C44-F22A \\sim C44-F23A \\sim C44-F24A
 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
 C43-F20 \\sim C43-F20A
 with sigma of 0.02
 C43-F19 \\sim C43-F19A
 with sigma of 0.02
 C43-F21 \\sim C43-F21A
 with sigma of 0.02
 C39-F20 \\sim C39-F20A
 with sigma of 0.04
 C39-F19 \\sim C39-F19A
 with sigma of 0.04
 C39-F21 \\sim C39-F21A
 with sigma of 0.04
 F20-F19 \\sim F20A-F19A
 with sigma of 0.04
 F20-F21 \\sim F20A-F21A
 with sigma of 0.04
 F19-F21 \\sim F19A-F21A
 with sigma of 0.04
 C43-F19 \\sim C43-F20 \\sim C43-F21
 with sigma of 0.02
 C43-F19A \\sim C43-F20A \\sim C43-F21A
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19
 with sigma of 0.02
 F19A-F20A \\sim F20A-F21A \\sim F21A-F19A
 with sigma of 0.02
 F48-C103 \\sim F48A-C103
 with sigma of 0.02
 F46-C103 \\sim F46A-C103
 with sigma of 0.02
 C103-F47 \\sim C103-F47A
 with sigma of 0.02
 C99-F48 \\sim C99-F48A
 with sigma of 0.04
 C99-F46 \\sim C99-F46A
 with sigma of 0.04
 C99-F47 \\sim C99-F47A
 with sigma of 0.04
 F48-F46 \\sim F48A-F46A
 with sigma of 0.04
 F48-F47 \\sim F48A-F47A
 with sigma of 0.04
 F46-F47 \\sim F46A-F47A
 with sigma of 0.04
 C103-F46 \\sim C103-F47 \\sim C103-F48
 with sigma of 0.02
 C103-F46A \\sim C103-F47A \\sim C103-F48A
 with sigma of 0.02
 F46-F47 \\sim F47-F48 \\sim F48-F46
 with sigma of 0.02
 F46A-F47A \\sim F47A-F48A \\sim F48A-F46A
 with sigma of 0.02
2. Restrained angles
 C54-C53-P3
 fixed at 117 with sigma of 0.02
3. Rigid bond restraints
 P3, C55, C56, C53, C54
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C87, F37, F39A, F38, F37A, F39, F38A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 P4, C61, C62, C59, C60
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C64, C69, C63, C68, C67, C72, C66, C71, C65, C70
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C43, F20A, F20, F19A, F19, F21A, F21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C95, F40A, F41, F42A, F40, F41A, F42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
P3 \\sim C55 \\sim C56 \\sim C53 \\sim C54: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
C28 \\sim F17 \\sim F16 \\sim F18: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 1.7A
C79 \\sim F30 \\sim F28 \\sim F29: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C87 \\sim F39A \\sim F38 \\sim F37A \\sim F39 \\sim F38A \\sim F37: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
P4 \\sim C61 \\sim C62 \\sim C59 \\sim C60: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
C64 \\sim C69 \\sim C63 \\sim C68 \\sim C67 \\sim C72 \\sim C66 \\sim C71 \\sim
C65 \\sim C70: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C80 \\sim F26 \\sim F25 \\sim F27: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C80 \\sim F26 \\sim F27 \\sim F25: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C88 \\sim F34 \\sim F36 \\sim F35: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C95 \\sim F42A \\sim F40 \\sim F41A \\sim F42 \\sim F41 \\sim F40A: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
C43 \\sim F20A \\sim F21 \\sim F21A \\sim F19 \\sim F19A \\sim F20: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
5. Rigid body (RIGU) restrains
 C28, F16, F17, F18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 P3, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C80, F26, F27, F25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79, F28, F29A, F30, F28A, F30A, F29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C80, F25, F26A, F27, F25A, F26, F27A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C95, F41, F40A, F42, F41A, F40, F42A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F42A)=Sof(F40A)=Sof(F41A)=1-FVAR(1)
 Sof(F42)=Sof(F41)=Sof(F40)=FVAR(1)
 Sof(F37A)=Sof(F38A)=Sof(F39A)=1-FVAR(2)
 Sof(F37)=Sof(F38)=Sof(F39)=FVAR(2)
 Sof(F17A)=Sof(F16A)=Sof(F18A)=1-FVAR(3)
 Sof(F18)=Sof(F17)=Sof(F16)=FVAR(3)
 Sof(F25A)=Sof(F27A)=Sof(F26A)=1-FVAR(4)
 Sof(F25)=Sof(F27)=Sof(F26)=FVAR(4)
 Sof(F28A)=Sof(F29A)=Sof(F30A)=1-FVAR(5)
 Sof(F30)=Sof(F29)=Sof(F28)=FVAR(5)
 Sof(F23A)=Sof(F22A)=Sof(F24A)=1-FVAR(6)
 Sof(F23)=Sof(F24)=Sof(F22)=FVAR(6)
 Sof(F21A)=Sof(F19A)=Sof(F20A)=1-FVAR(7)
 Sof(F20)=Sof(F19)=Sof(F21)=FVAR(7)
 Sof(F47A)=Sof(F46A)=Sof(F48A)=1-FVAR(8)
 Sof(F48)=Sof(F46)=Sof(F47)=FVAR(8)
7.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C16(H16A,H16B), C17(H17A,H17B), C15(H15A,H15B), C57(H57A,
 H57B), C13(H13A,H13B), C58(H58A,H58B), C59(H59A,H59B), C11(H11A,H11B),
 C55(H55A,H55B), C53(H53A,H53B), C61(H61A,H61B)
7.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C102(H102), C42(H42), C34(H34), C46(H46), C22(H22), C32(H32),
 C100(H100), C38(H38), C90(H90), C50(H50), C94(H94), C26(H26), C98(H98),
 C40(H40), C24(H24), C74(H74), C48(H48), C92(H92), C78(H78), C82(H82), C86(H86),
  C76(H76), C84(H84)
7.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C9(H9A,H9B,H9C), C6(H6A,H6B,H6C), C20(H20A,H20B,H20C), C68(H68A,H68B,H68C),
 C14(H14A,H14B,H14C), C69(H69A,H69B,H69C), C12(H12A,H12B,H12C), C60(H60A,H60B,
 H60C), C62(H62A,H62B,H62C), C72(H72A,H72B,H72C), C71(H71A,H71B,H71C), C70(H70A,
 H70B,H70C), C56(H56A,H56B,H56C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              39299
_shelx_hkl_checksum              58382
_olex2_submission_special_instructions 'No special instructions were received'