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_1576453
_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
'Ce N6 O18, 2(C39 H24 Fe N3), 4(C4 H10 O2), H4 N'
_chemical_formula_sum            'C94 H92 Ce Fe2 N13 O26'
_chemical_formula_weight         2071.62
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-05-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2026-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                105.165(2)
_cell_angle_beta                 106.901(3)
_cell_angle_gamma                101.067(2)
_cell_formula_units_Z            1
_cell_length_a                   11.9758(3)
_cell_length_b                   13.1767(3)
_cell_length_c                   16.3831(4)
_cell_measurement_reflns_used    20218
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3290
_cell_measurement_theta_min      3.0080
_cell_volume                     2284.72(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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 0.992
_diffrn_measured_fraction_theta_max 0.974
_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    -95.00 -13.00   0.50    3.04    --  -49.12 130.00 124.00  164
  2  \w   -102.00 -18.00   0.50    3.04    --  -49.12 140.00 -61.00  168
  3  \w   -120.00 -60.00   0.50    3.04    --  -49.12-140.00-120.00  120
  4  \w   -120.00 -67.00   0.50    3.04    --  -49.12-130.00  52.00  106
  5  \w     40.00 103.00   0.50    3.04    --   49.12-140.00-120.00  126
  6  \w     34.00  97.00   0.50    3.04    --   49.12-130.00  52.00  126
  7  \w   -102.00 -18.00   0.50   12.18    --  -84.25 140.00 -61.00  168
  8  \w    -94.00 -13.00   0.50   12.18    --  -84.25 130.00 124.00  162
  9  \w     82.00 178.00   0.50   12.18    --  105.75 140.00 -61.00  192
 10  \w     40.00 128.00   0.50   12.18    --  105.75-140.00-120.00  176
 11  \w     34.00 120.00   0.50   12.18    --  105.75-130.00  52.00  172
 12  \w     89.00 178.00   0.50   12.18    --  105.75 130.00 124.00  178
 13  \w   -120.00 -70.00   0.50    3.04    --  -49.12-125.00 -90.00  100
 14  \w   -120.00 -70.00   0.50    3.04    --  -49.12-125.00-150.00  100
 15  \w   -120.00 -36.00   0.50    3.04    --  -49.12 -57.00 -90.00  168
 16  \w    -30.00  22.00   0.50    3.04    --  -49.12  38.00  30.00  104
 17  \w   -120.00 -28.00   0.50    3.04    --  -49.12 -77.00-120.00  184
 18  \w    -23.00   5.00   0.50    3.04    --   49.12 -19.00  60.00   56
 19  \w   -156.00 -67.00   0.50   12.18    --  -84.25-130.00  52.00  178
 20  \w   -156.00 -60.00   0.50   12.18    --  -84.25-140.00-120.00  192
 21  \w     98.00 164.00   0.50   12.18    --  105.75  15.00 -30.00  132
 22  \w     34.00 116.00   0.50   12.18    --  105.75-125.00 150.00  164
 23  \w     92.00 178.00   0.50   12.18    --  105.75  61.00-150.00  172
 24  \w     34.00 109.00   0.50   12.18    --  105.75 -94.00 -90.00  150
 25  \w     98.00 178.00   0.50   12.18    --  105.75  30.00   0.00  160
 26  \w     98.00 164.00   0.50   12.18    --  105.75  15.00 -90.00  132
 27  \w     34.00  87.00   0.50   12.18    --  105.75 -61.00 -90.00  106
 28  \w     34.00 116.00   0.50   12.18    --  105.75-125.00  90.00  164
 29  \w     34.00  87.00   0.50   12.18    --  105.75 -61.00  90.00  106
 30  \w     34.00 127.00   0.50   12.18    --  105.75 -77.00 150.00  186
 31  \w     34.00  87.00   0.50   12.18    --  105.75 -61.00 -60.00  106
 32  \w     98.00 178.00   0.50   12.18    --  105.75  30.00 -90.00  160
 33  \w     34.00 109.00   0.50   12.18    --  105.75 -94.00 -60.00  150
 34  \w     34.00 116.00   0.50   12.18    --  105.75-125.00-180.00  164
 35  \w     97.00 178.00   0.50   12.18    --  105.75  45.00-180.00  162
 36  \w     34.00 109.00   0.50   12.18    --  105.75 -94.00-120.00  150
 37  \w     40.00 111.00   0.50   12.18    --  105.75-125.00  30.00  142
 38  \w    101.00 165.00   0.50   12.18    --  105.75  30.00 120.00  128
 39  \w     95.00 176.00   0.50   12.18    --  105.75 125.00-180.00  162
 40  \w     35.00  74.00   0.50   12.18    --  105.75 -61.00   0.00   78
 41  \w     90.00 116.00   0.50   12.18    --  105.75-125.00 -90.00   52
 42  \w     42.00  75.00   0.50   12.18    --  105.75-125.00 -90.00   66
 43  \w     53.00  80.00   0.50   12.18    --  105.75-125.00 120.00   54
 44  \w     91.00 116.00   0.50   12.18    --  105.75-125.00 120.00   50
 45  \w    108.00 155.00   0.50   12.18    --  105.75  61.00 -60.00   94
 46  \w    101.00 127.00   0.50   12.18    --  105.75-138.00  -6.91   52
 47  \w     35.00  84.00   0.50   12.18    --  105.75 -94.00 150.00   98
 48  \w     34.00  61.00   0.50   12.18    --  105.75-125.00-150.00   54
 49  \w     82.00 116.00   0.50   12.18    --  105.75-125.00-150.00   68
 50  \w    105.00 161.00   0.50   12.18    --  105.75  15.00 -60.00  112
 51  \w     44.00  74.00   0.50   12.18    --  105.75 -94.00-150.00   60
 52  \w     35.00  76.00   0.50   12.18    --  105.75 -61.00  60.00   82
 53  \w     90.00 116.00   0.50   12.18    --  105.75-125.00 -30.00   52
 54  \w     48.00  87.00   0.50   12.18    --  105.75 -61.00-120.00   78
;
_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      0.0564239000
_diffrn_orient_matrix_UB_12      0.1144731000
_diffrn_orient_matrix_UB_13      -0.0016565000
_diffrn_orient_matrix_UB_21      -0.0568077000
_diffrn_orient_matrix_UB_22      -0.0431669000
_diffrn_orient_matrix_UB_23      -0.1043020000
_diffrn_orient_matrix_UB_31      -0.1154434000
_diffrn_orient_matrix_UB_32      0.0324863000
_diffrn_orient_matrix_UB_33      0.0047763000
_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  0.0752
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            53682
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.895
_diffrn_reflns_theta_min         3.632
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.019
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown-green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       plate
_exptl_crystal_F_000             1065
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.115
_exptl_crystal_size_min          0.029
_refine_diff_density_max         1.618
_refine_diff_density_min         -1.904
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     680
_refine_ls_number_reflns         9500
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0717
_refine_ls_R_factor_gt           0.0596
_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^)+(0.1091P)^2^+1.9089P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1608
_refine_ls_wR_factor_ref         0.1703
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7795
_reflns_number_total             9500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08832a2.cif
_cod_data_source_block           neinw66
_cod_depositor_comments
'Adding full bibliography for 1576451--1576463.cif.'
_cod_original_cell_volume        2284.72(10)
_cod_database_code               1576453
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.425
_reflns_odcompleteness_completeness 99.19
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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, All N(H,H,H,H) groups
2. 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
3. Rigid body (RIGU) restrains
 C40, O10, C41, C42, O11, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40', O10', C41', C42', O11', C43'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C43, O11, C42, C41, O10, C40} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C40, O10, C41, C42, O11, C43}
{C40, O10, C41, C42, O11, C43} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C40', O10', C41', C42', O11', C43'}
5. Others
 Sof(C40')=Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(O10')=Sof(C41')=Sof(H41C)=
 Sof(H41D)=Sof(C42')=Sof(H42C)=Sof(H42D)=Sof(O11')=Sof(C43')=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=1-FVAR(1)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(O10)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(O11)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 FVAR(1)
 Fixed Sof: N7(0.5) H7A(0.5) H7B(0.5) H7C(0.5) H7D(0.5)
6.a Riding coordinates:
 N7(H7A,H7B,H7C,H7D)
6.b Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C42(H42A,H42B), C45(H45A,H45B), C46(H46A,H46B), C41'(H41C,
 H41D), C42'(H42C,H42D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C28(H28),
  C29(H29), C30(H30), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37)
6.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C47(H47A,H47B,
 H47C), C40'(H40D,H40E,H40F), C43'(H43D,H43E,H43F)
;
_shelx_res_checksum              28606
_olex2_submission_original_sample_id neinw66
_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 2.249
_oxdiff_exptl_absorpt_empirical_full_min 0.454