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_1576779
_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 N2 P2, C32 H12 B F24'
_chemical_formula_sum            'C52 H51 B F24 Fe N2 P2'
_chemical_formula_weight         1288.54
_chemical_name_systematic        C52H51BF24FeN2P2
_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             2025-07-22
_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                96.758(2)
_cell_angle_beta                 90.524(2)
_cell_angle_gamma                96.518(2)
_cell_formula_units_Z            2
_cell_length_a                   12.3633(7)
_cell_length_b                   12.7575(7)
_cell_length_c                   18.6259(11)
_cell_measurement_reflns_used    9499
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      26.05
_cell_measurement_theta_min      2.18
_cell_volume                     2897.7(3)
_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)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  D8Quest_IIQ
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0976
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_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       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            122997
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.175
_diffrn_reflns_theta_min         2.012
_exptl_absorpt_coefficient_mu    0.429
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6411
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1136 before and 0.0735 after correction.
The Ratio of minimum to maximum transmission is 0.8600.
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    1.477
_exptl_crystal_description       plate
_exptl_crystal_F_000             1308
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.383
_refine_diff_density_min         -1.135
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     845
_refine_ls_number_reflns         12852
_refine_ls_number_restraints     243
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1312
_refine_ls_R_factor_gt           0.0940
_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^)+(0.1372P)^2^+7.2365P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2508
_refine_ls_wR_factor_ref         0.2862
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8708
_reflns_number_total             12852
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07656k2.cif
_cod_data_source_block           complex2
_cod_depositor_comments
'Adding full bibliography for 1576777--1576784.cif.'
_cod_database_code               1576779
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.958
_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
 C15-P1
 1.89 with sigma of 0.00002
 C16-C15
 1.51 with sigma of 0.005
 P1-Fe1
 2.25 with sigma of 0.0005
 C52-F23
 1.3 with sigma of 0.02
 C52-F22A
 1.3 with sigma of 0.02
 C52-F24
 1.3 with sigma of 0.02
 C52-F23A
 1.3 with sigma of 0.02
 C52-F22
 1.3 with sigma of 0.02
 C52-F24A
 1.3 with sigma of 0.02
 C19-C20
 1.53 with sigma of 0.02
 P1-C15 \\sim P2-C16
 with sigma of 0.001
 P2-C17 \\sim P2-C19
 with sigma of 0.02
 P2-C18 \\sim P2-C20
 with sigma of 0.02
 P1-C11 \\sim P1-C13
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22
 with sigma of 0.02
 P1-C12 \\sim P1-C14
 with sigma of 0.01
 C35-F8 \\sim C35-F8A
 with sigma of 0.02
 F22A-F23A \\sim F23A-F24A \\sim F24A-F22A
 with sigma of 0.02
 C52-F22 \\sim C52-F23 \\sim C52-F24
 with sigma of 0.02
 C52-F22A \\sim C52-F23A \\sim C52-F24A
 with sigma of 0.02
 F20-C51 \\sim F20A-C51
 with sigma of 0.02
 C35-F9 \\sim C35-F9A
 with sigma of 0.02
 C51-F21 \\sim C51-F21A
 with sigma of 0.02
 C51-F19 \\sim C51-F19A
 with sigma of 0.02
 C35-F7 \\sim C35-F7A
 with sigma of 0.02
 F17-C44 \\sim F17A-C44
 with sigma of 0.02
 C47-F20 \\sim C47-F20A \\sim C47-F21 \\sim C47-F21A \\sim C47-F19 \\sim
C47-F19A
 with sigma of 0.04
 F16-C44 \\sim F16A-C44
 with sigma of 0.02
 F20-F21 \\sim F20A-F21A
 with sigma of 0.04
 F20-F19 \\sim F20A-F19A
 with sigma of 0.04
 C44-F18 \\sim C44-F18A
 with sigma of 0.02
 F21-F19 \\sim F21A-F19A
 with sigma of 0.04
 C41-F17 \\sim C41-F17A
 with sigma of 0.04
 C41-F16 \\sim C41-F16A
 with sigma of 0.04
 C51-F19 \\sim C51-F20 \\sim C51-F21
 with sigma of 0.02
 C41-F18 \\sim C41-F18A
 with sigma of 0.04
 C51-F19A \\sim C51-F20A \\sim C51-F21A
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19
 with sigma of 0.02
 F17-F16 \\sim F17A-F16A
 with sigma of 0.04
 F17-F18 \\sim F17A-F18A
 with sigma of 0.04
 F19A-F20A \\sim F20A-F21A \\sim F21A-F19A
 with sigma of 0.02
 F16-F18 \\sim F16A-F18A
 with sigma of 0.04
 C44-F16 \\sim C44-F17 \\sim C44-F18
 with sigma of 0.02
 C44-F16A \\sim C44-F17A \\sim C44-F18A
 with sigma of 0.02
 F16-F17 \\sim F17-F18 \\sim F18-F16
 with sigma of 0.02
 F16A-F17A \\sim F17A-F18A \\sim F18A-F16A
 with sigma of 0.02
3. Rigid bond restraints
 N2, N1
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 P2, C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Fe1, P1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C52, F23A, F23, F24A, F22, F22A, F24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N2 \\sim N1: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
P2 \\sim C19 \\sim C20: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
Fe1 \\sim P1: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 1.7A
C52 \\sim F23 \\sim F22A \\sim F24 \\sim F23A \\sim F24A \\sim F22: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
5. Rigid body (RIGU) restrains
 Fe1, P2, C16, C15, P1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C52, F23, F22A, F23A, F24, F22, F24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(1)
 Sof(F8)=Sof(F9)=Sof(F7)=FVAR(1)
 Sof(F18A)=Sof(F16A)=Sof(F17A)=1-FVAR(2)
 Sof(F17)=Sof(F16)=Sof(F18)=FVAR(2)
 Sof(F21A)=Sof(F20A)=Sof(F19A)=1-FVAR(3)
 Sof(F20)=Sof(F21)=Sof(F19)=FVAR(3)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(4)
 Sof(F24)=Sof(F22)=Sof(F23)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C11(H11A,H11B), C16(H16A,H16B), C15(H15A,H15B), C13(H13A,
 H13B), C19(H19A,H19B)
7.b Aromatic/amide H refined with riding coordinates:
 C42(H42), C34(H34), C38(H38), C30(H30), C22(H22), C40(H40), C32(H32),
 C46(H46), C50(H50), C26(H26), C24(H24), C48(H48)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C),
 C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C12(H12A,H12B,H12C), C20(H20A,H20B,H20C),
  C14(H14A,H14B,H14C)
;
_shelx_res_checksum              9266
_shelx_hkl_checksum              15310
_olex2_submission_special_instructions 'No special instructions were received'