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_1576782
_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 H37 Fe P2, C32 H12 B F24'
_chemical_formula_sum            'C52 H49 B F24 Fe P2'
_chemical_formula_weight         1258.51
_chemical_name_systematic        C52H49BF24FeP2
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-18
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7221)
;
_audit_update_record
;
2025-07-23 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                78.220(6)
_cell_angle_beta                 69.724(6)
_cell_angle_gamma                78.417(6)
_cell_formula_units_Z            2
_cell_length_a                   12.801(2)
_cell_length_b                   13.0443(18)
_cell_length_c                   17.892(3)
_cell_measurement_reflns_used    9797
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      27.430
_cell_measurement_theta_min      2.404
_cell_volume                     2715.8(7)
_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      110.00
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  D8Quest_IIQ
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1221
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_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       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            122496
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.082
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.455
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5997
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1298 before and 0.0876 after correction.
The Ratio of minimum to maximum transmission is 0.8043.
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    1.539
_exptl_crystal_description       plate
_exptl_crystal_F_000             1276
_exptl_crystal_preparation       'toluene -30dregrees'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.250
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     813
_refine_ls_number_reflns         11101
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0911
_refine_ls_R_factor_gt           0.0668
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0642P)^2^+6.7990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1557
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8452
_reflns_number_total             11101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07656k2.cif
_cod_data_source_block           jcm24524a_0m
_cod_depositor_comments
'Adding full bibliography for 1576777--1576784.cif.'
_cod_original_cell_volume        2715.9(7)
_cod_database_code               1576782
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.914
_diffrn_oxdiff_ac3_digest_hkl    41db6853efff2a27efece4df567d2293368116
_olex2_refinement_description
;
1. Restrained distances
 F6-C28
 1.31 with sigma of 0.02
 C52-F22
 1.29 with sigma of 0.02
 C52-F24
 1.36 with sigma of 0.02
 C52-F23
 1.27 with sigma of 0.02
 C28-F5
 1.31 with sigma of 0.02
 C28-F4
 1.31 with sigma of 0.02
 F12-C35
 1.31 with sigma of 0.02
 F10A-C35
 1.31 with sigma of 0.02
 F11-C35
 1.31 with sigma of 0.02
 F12A-C35
 1.31 with sigma of 0.02
 F10-C35
 1.31 with sigma of 0.02
 F11A-C35
 1.31 with sigma of 0.02
 C35-F10A
 1.31 with sigma of 0.02
 C35-F12
 1.31 with sigma of 0.02
 C35-F11A
 1.31 with sigma of 0.02
 C35-F10
 1.31 with sigma of 0.02
 C35-F12A
 1.31 with sigma of 0.02
 C35-F11
 1.31 with sigma of 0.02
 F10-C35 \\sim F10A-C35
 with sigma of 0.02
 C35-F11 \\sim C35-F11A
 with sigma of 0.02
 C52-F22 \\sim C52-F24 \\sim C52-F23
 with sigma of 0.02
 C52-F22 \\sim C52-F22A
 with sigma of 0.02
 C35-F12 \\sim C35-F12A
 with sigma of 0.02
 C52-F24 \\sim C52-F23A
 with sigma of 0.02
 F4-C28 \\sim F4A-C28
 with sigma of 0.02
 C52-F23 \\sim C52-F24A
 with sigma of 0.02
 C35-F10 \\sim C35-F11 \\sim C35-F12
 with sigma of 0.02
 F6-C28 \\sim F6A-C28
 with sigma of 0.02
 F5-C28 \\sim F5A-C28
 with sigma of 0.02
 C35-F10A \\sim C35-F11A \\sim C35-F12A
 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
 C28-F4 \\sim C28-F5 \\sim C28-F6
 with sigma of 0.02
 F10-F11 \\sim F11-F12 \\sim F12-F11
 with sigma of 0.02
 C28-F4A \\sim C28-F5A \\sim C28-F6A
 with sigma of 0.02
 F10A-F11A \\sim F11A-F12A \\sim F12A-F11A
 with sigma of 0.02
 F22-F24 \\sim F24-F23 \\sim F23-F22
 with sigma of 0.03
2. Restrained angles
 F17-C43-F18, F10A-C35-F10
 fixed at 106.6 with sigma of 0.02
3. Rigid bond restraints
 C52, F22, F23, F24
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C52, F22A, F23A, F24A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28, F4A, F4, F6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28, F5A, F6A, F5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28, F4, F5, F6
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C28, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C35, F10, F11, F12
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C35, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C52 \\sim F22 \\sim F23 \\sim F24: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 1.7A
C52 \\sim F22A \\sim F23A \\sim F24A: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 1.7A
C28 \\sim F4A \\sim F4 \\sim F6: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C28 \\sim F5A \\sim F6A \\sim F5: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C28 \\sim F4 \\sim F5 \\sim F6: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C28 \\sim F4A \\sim F5A \\sim F6A: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C35 \\sim F10 \\sim F11 \\sim F12: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C35 \\sim F10A \\sim F11A \\sim F12A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.7A
Uanis(F10A) \\sim Ueq, Uanis(F10) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C35, F10A, F11A, F12A, F10, F11, F12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35, F10A, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C11(H11)
7.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C19(H19A,H19B)
7.c 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.d 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), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              38751
_shelx_hkl_checksum              33348
_olex2_submission_special_instructions 'No special instructions were received'