Iron tris-mesityl: a homoleptic iron(ii) ferrate species for directed C–H activation
Radović, Aleksa; Healy, Maria C.; Datta, Arnadeep; Das, Deborshee; Cai, Likun; Diaz, Steven; Gogoi, Achyut Ranjan; Wolford, Nikki J.; Carpenter, Stephanie H.; Brenessel, William W.; McCamant, David; Gutierrez, Osvaldo; Neidig, Michael L.; Chemical Science  (2026) –; doi:10.1039/D5SC08832A

data_1576452
_publ_section_title
;
 Iron tris-mesityl: a homoleptic iron(ii) ferrate species for directed C-H
 activation.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              7002
_journal_page_last               7009
_journal_paper_doi               10.1039/d5sc08832a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C33 H24 Fe N3, C18 H36 K N2 O6, 2(C4 H8 O)'
_chemical_formula_sum            'C59 H76 Fe K N5 O8'
_chemical_formula_weight         1078.19
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-05-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2026-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                91.8400(10)
_cell_angle_beta                 90.5310(10)
_cell_angle_gamma                93.0570(10)
_cell_formula_units_Z            2
_cell_length_a                   12.9303(2)
_cell_length_b                   13.4933(2)
_cell_length_c                   15.5169(2)
_cell_measurement_reflns_used    37120
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.6690
_cell_measurement_theta_min      3.2920
_cell_volume                     2701.86(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -120.00 -51.00   0.50    0.72    --  -47.29-158.00 -97.00  138
  2  \w   -108.00 -30.00   0.50    0.72    --  -47.29 158.00 -63.00  156
  3  \w    -84.00  -9.00   0.50    0.72    --  -47.29 119.00 142.00  150
  4  \w     73.00 120.00   0.50    0.72    --   47.29 158.00 -63.00   94
  5  \w     30.00  92.00   0.50    0.72    --   47.29-119.00  56.00  124
  6  \w     51.00 115.00   0.50    0.72    --   47.29-158.00 -97.00  128
  7  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00-150.00   88
  8  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00  90.00   88
  9  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00-120.00   88
 10  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00 120.00   88
 11  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00   0.00   88
 12  \w    -16.00  28.00   0.50    0.72    --  -47.29  19.00 -30.00   88
 13  \w   -120.00 -73.00   0.50    0.72    --  -47.29-125.00  90.00   94
 14  \w   -120.00 -73.00   0.50    0.72    --  -47.29-125.00-150.00   94
 15  \w     25.00 120.00   0.50    0.72    --   47.29  77.00 -60.00  190
 16  \w     25.00 120.00   0.50    0.72    --   47.29  77.00-120.00  190
 17  \w     25.00 120.00   0.50    0.72    --   47.29  77.00   0.00  190
 18  \w     32.00 120.00   0.50    0.72    --   47.29  57.00-150.00  176
 19  \w     25.00 120.00   0.50    0.72    --   47.29  77.00 120.00  190
 20  \w     25.00 120.00   0.50    0.72    --   47.29  77.00-180.00  190
 21  \w     32.00 120.00   0.50    0.72    --   47.29  57.00 -30.00  176
 22  \w     35.00 120.00   0.50    0.72    --   47.29  38.00  90.00  170
 23  \w     35.00 120.00   0.50    0.72    --   47.29  38.00-180.00  170
 24  \w     35.00 120.00   0.50    0.72    --   47.29  38.00 -60.00  170
 25  \w     25.00 120.00   0.50    0.72    --   47.29  77.00 -30.00  190
 26  \w     25.00 120.00   0.50    0.72    --   47.29  77.00  60.00  190
 27  \w    -84.00 -19.00   0.50    2.90    --  -91.75 119.00 142.00  130
 28  \w   -109.00 -30.00   0.50    2.90    --  -91.75 158.00 -63.00  158
 29  \w   -163.00 -77.00   0.50    2.90    --  -91.75-119.00  56.00  172
 30  \w   -163.00 -79.00   0.50    2.90    --  -91.75 -45.00 120.00  168
 31  \w    -65.00 -19.00   0.50    2.90    --  -91.75  61.00 -60.00   92
 32  \w   -163.00-119.00   0.50    2.90    --  -91.75 -75.00 -77.20   88
 33  \w   -163.00 -69.00   0.50    2.90    --  -91.75 -76.00  96.33  188
 34  \w   -163.00 -69.00   0.50    2.90    --  -91.75 -77.00   0.00  188
 35  \w   -163.00 -69.00   0.50    2.90    --  -91.75 -77.00-120.00  188
 36  \w     99.00 178.00   0.50    2.90    --  113.25 119.00 142.00  158
 37  \w     73.00 160.00   0.50    2.90    --  113.25 158.00 -63.00  174
 38  \w     51.00 135.00   0.50    2.90    --  113.25-158.00 -97.00  168
 39  \w     42.00 110.00   0.50    2.90    --  113.25-119.00  56.00  136
 40  \w     42.00  79.00   0.50    2.90    --  113.25 -61.00  30.00   74
 41  \w     42.00 111.00   0.50    2.90    --  113.25-125.00 150.00  138
 42  \w     42.00 111.00   0.50    2.90    --  113.25-125.00-120.00  138
 43  \w     95.00 178.00   0.50    2.90    --  113.25 125.00  90.00  166
 44  \w    100.00 178.00   0.50    2.90    --  113.25  15.00 -30.00  156
 45  \w    101.00 178.00   0.50    2.90    --  113.25  30.00-120.00  154
 46  \w     97.00 178.00   0.50    2.90    --  113.25  61.00  30.00  162
 47  \w    101.00 178.00   0.50    2.90    --  113.25  45.00  60.00  154
 48  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00 -90.00  128
 49  \w     42.00 111.00   0.50    2.90    --  113.25-125.00  90.00  138
 50  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00-120.00  128
 51  \w     42.00  79.00   0.50    2.90    --  113.25 -61.00-150.00   74
 52  \w     97.00 178.00   0.50    2.90    --  113.25  61.00 -60.00  162
 53  \w     97.00 178.00   0.50    2.90    --  113.25  61.00   0.00  162
 54  \w     42.00  79.00   0.50    2.90    --  113.25 -61.00 120.00   74
 55  \w    100.00 178.00   0.50    2.90    --  113.25  15.00 120.00  156
 56  \w    100.00 178.00   0.50    2.90    --  113.25  15.00-180.00  156
 57  \w     42.00 111.00   0.50    2.90    --  113.25-125.00-180.00  138
 58  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00  90.00  128
 59  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00  30.00  128
 60  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00-150.00  128
 61  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00 -60.00  128
 62  \w     42.00 111.00   0.50    2.90    --  113.25-125.00  30.00  138
 63  \w     42.00  79.00   0.50    2.90    --  113.25 -61.00  60.00   74
 64  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00 120.00  128
 65  \w    101.00 178.00   0.50    2.90    --  113.25  45.00 -90.00  154
 66  \w     95.00 178.00   0.50    2.90    --  113.25 125.00 -60.00  166
 67  \w     42.00 106.00   0.50    2.90    --  113.25 -94.00 -30.00  128
 68  \w     42.00 106.00   0.50    2.90    --  113.25 -95.00 136.57  128
 69  \w     42.00 111.00   0.50    2.90    --  113.25-125.00 120.00  138
 70  \w    101.00 178.00   0.50    2.90    --  113.25  45.00-180.00  154
 71  \w     42.00  79.00   0.50    2.90    --  113.25 -61.00-120.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1166866000
_diffrn_orient_matrix_UB_12      -0.0083956000
_diffrn_orient_matrix_UB_13      -0.0158818000
_diffrn_orient_matrix_UB_21      0.0180771000
_diffrn_orient_matrix_UB_22      -0.0129739000
_diffrn_orient_matrix_UB_23      0.0971670000
_diffrn_orient_matrix_UB_31      -0.0171742000
_diffrn_orient_matrix_UB_32      -0.1133477000
_diffrn_orient_matrix_UB_33      -0.0132191000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0632
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            91029
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.614
_diffrn_reflns_theta_min         3.282
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.409
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64132
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange-black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       plate
_exptl_crystal_F_000             1148
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.677
_refine_diff_density_min         -0.748
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     785
_refine_ls_number_reflns         11619
_refine_ls_number_restraints     162
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0550
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0940P)^2^+1.3682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1542
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10296
_reflns_number_total             11619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08832a2.cif
_cod_data_source_block           neiar11
_cod_depositor_comments
'Adding full bibliography for 1576451--1576463.cif.'
_cod_database_code               1576452
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N4-C46 \\sim N4-C46' \\sim N5-C39 \\sim N5'-C39' \\sim N5-C45 \\sim N5'-C45
 with sigma of 0.02
 C44-O4 \\sim C44'-O4 \\sim C38-O2 \\sim C38'-O2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
4. Same fragment restrains
{N5, C39, C38} sigma for 1-2: 0.02, 1-3: 0.04
{N5', C39', C38'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5', C45', C44'}
{C46, C47, O5, C48, C49, O6, C50, C51, C45, C44} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C46', C47', O5', C48', C49', O6', C50', C51', O7, C52}
5. Others
 Sof(N5')=Sof(C45')=Sof(H45A)=Sof(H45B)=Sof(C44')=Sof(H44A)=Sof(H44B)=
 Sof(C39')=Sof(H39C)=Sof(H39D)=Sof(C38')=Sof(H38C)=Sof(H38D)=Sof(C46')=
 Sof(H46C)=Sof(H46D)=Sof(C47')=Sof(H47C)=Sof(H47D)=Sof(O5')=Sof(C48')=Sof(H48C)=
 Sof(H48D)=Sof(C49')=Sof(H49C)=Sof(H49D)=Sof(O6')=Sof(C50')=Sof(H50C)=Sof(H50D)=
 Sof(C51')=Sof(H51C)=Sof(H51D)=1-FVAR(1)
 Sof(N5)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(O5)=Sof(C48)=Sof(H48A)=
 Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(O6)=Sof(C50)=Sof(H50A)=Sof(H50B)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C45)=Sof(H45C)=Sof(H45D)=Sof(C44)=Sof(H44C)=
 Sof(H44D)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C39(H39A,
 H39B), C38(H38A,H38B), C45'(H45A,H45B), C44'(H44A,H44B), C39'(H39C,H39D),
 C38'(H38C,H38D), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,
 H43B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B),
 C50(H50A,H50B), C51(H51A,H51B), C45(H45C,H45D), C44(H44C,H44D), C46'(H46C,
 H46D), C47'(H47C,H47D), C48'(H48C,H48D), C49'(H49C,H49D), C50'(H50C,H50D),
 C51'(H51C,H51D), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,
 H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32), C33(H33)
;
_shelx_res_checksum              53618
_olex2_submission_original_sample_id neiar11
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.475
_oxdiff_exptl_absorpt_empirical_full_min 0.676