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_1576456
_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         'C27 H33 Fe, C20 H40 Br Mg O5'
_chemical_formula_sum            'C47 H73 Br Fe Mg O5'
_chemical_formula_weight         878.12
_chemical_name_systematic        012mch25
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2026-01-12 deposited with the CCDC.	2026-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.467(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4231(3)
_cell_length_b                   17.6759(5)
_cell_length_c                   21.3412(6)
_cell_measurement_reflns_used    14918
_cell_measurement_temperature    149.9(3)
_cell_measurement_theta_max      76.1430
_cell_measurement_theta_min      4.2750
_cell_volume                     4665.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.971
_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   -111.00 -15.00   1.00    5.50    --  -41.90 -57.00 120.00   96
  2  \w    -44.00  20.00   1.00    5.50    --  -41.90  57.00-120.00   64
  3  \w     -2.00  27.00   1.00    5.50    --  -41.90  19.00 -60.00   29
  4  \w      7.00  33.00   1.00    5.50    --  -41.90  19.00-150.00   26
  5  \w     58.00  87.00   1.00    5.50    --   41.90-125.00-150.00   29
  6  \w    108.00 150.00   1.00   22.00    --  111.00  77.00-120.00   42
  7  \w     42.00  69.00   1.00   22.00    --  111.00 -45.00 -90.00   27
  8  \w     91.00 177.00   1.00   22.00    --  111.00  30.00-150.00   86
  9  \w     40.00  72.00   1.00   22.00    --  111.00 -45.00-150.00   32
 10  \w     42.00  71.00   1.00   22.00    --  111.00 -45.00  90.00   29
 11  \w     48.00  93.00   1.00   22.00    --  111.00 -61.00  60.00   45
 12  \w    140.00 166.00   1.00   22.00    --  111.00 125.00 -60.00   26
 13  \w     75.00 112.00   1.00   22.00    --  111.00-125.00 -90.00   37
 14  \w    114.00 163.00   1.00   22.00    --  111.00  77.00 120.00   49
 15  \w     30.00  56.00   1.00   22.00    --  111.00 -94.00  90.00   26
 16  \w     57.00 112.00   1.00   22.00    --  111.00-125.00-120.00   55
 17  \w     77.00 105.00   1.00   22.00    --  111.00 -94.00  90.00   28
 18  \w    105.00 175.00   1.00   22.00    --  111.00  15.00 -30.00   70
 19  \w     41.00  79.00   1.00   22.00    --  111.00-125.00 -30.00   38
 20  \w     42.00  68.00   1.00   22.00    --  111.00 -45.00 120.00   26
 21  \w     64.00 107.00   1.00   22.00    --  111.00 -94.00 150.00   43
 22  \w     80.00 107.00   1.00   22.00    --  111.00 -94.00 120.00   27
 23  \w     47.00  72.00   1.00   22.00    --  111.00 -45.00-180.00   25
 24  \w     -3.00  35.00   1.00    5.50    --  -41.90  19.00  90.00   38
 25  \w     -4.00  22.00   1.00    5.50    --  -41.90  19.00-120.00   26
 26  \w    -78.00  -9.00   1.00    5.50    --  -41.90 125.00 -90.00   69
 27  \w    -17.00  30.00   1.00    5.50    --  -41.90  37.00-180.00   47
 28  \w     14.00  76.00   1.00    5.50    --   41.90 -99.00  30.00   62
 29  \w    117.00 155.00   1.00   22.00    --  111.00  45.00-120.00   38
 30  \w    109.00 142.00   1.00   22.00    --  111.00  77.00  90.00   33
 31  \w     31.00  57.00   1.00   22.00    --  111.00 -94.00 -60.00   26
 32  \w     77.00 112.00   1.00   22.00    --  111.00-125.00 -30.00   35
 33  \w     82.00 107.00   1.00   22.00    --  111.00 -94.00-120.00   25
 34  \w     41.00  68.00   1.00   22.00    --  111.00-125.00 120.00   27
 35  \w     86.00 112.00   1.00   22.00    --  111.00-125.00 120.00   26
 36  \w    103.00 136.00   1.00   22.00    --  111.00  77.00 -30.00   33
 37  \w     42.00  71.00   1.00   22.00    --  111.00 -45.00   0.00   29
 38  \w    117.00 158.00   1.00   22.00    --  111.00  30.00  30.00   41
 39  \w     30.00  55.00   1.00   22.00    --  111.00 -94.00-120.00   25
 40  \w     53.00  90.00   1.00   22.00    --  111.00 -61.00 -60.00   37
 41  \w     40.00  66.00   1.00   22.00    --  111.00 -45.00  60.00   26
 42  \w     43.00  69.00   1.00   22.00    --  111.00 -77.00 -90.00   26
 43  \w     58.00  90.00   1.00   22.00    --  111.00 -61.00   0.00   32
 44  \w     75.00 106.00   1.00   22.00    --  111.00 -94.00  30.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0219454000
_diffrn_orient_matrix_UB_12      -0.0857925000
_diffrn_orient_matrix_UB_13      0.0014319000
_diffrn_orient_matrix_UB_21      0.0868454000
_diffrn_orient_matrix_UB_22      0.0110782000
_diffrn_orient_matrix_UB_23      0.0557522000
_diffrn_orient_matrix_UB_31      -0.0865813000
_diffrn_orient_matrix_UB_32      -0.0107207000
_diffrn_orient_matrix_UB_33      0.0463347000
_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  0.0925
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41369
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.003
_diffrn_reflns_theta_min         3.961
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.047
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.295
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       needle
_exptl_crystal_F_000             1872
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.771
_refine_diff_density_min         -1.030
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     505
_refine_ls_number_reflns         9585
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0593
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0506P)^2^+6.4072P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1344
_refine_ls_wR_factor_ref         0.1486
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6868
_reflns_number_total             9585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08832a2.cif
_cod_data_source_block           012mch-25
_cod_depositor_comments
'Adding full bibliography for 1576451--1576463.cif.'
_cod_database_code               1576456
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C47 H76 Br Fe Mg1 O4'
_cell_oxdiff_angle_alpha         89.970(3)
_cell_oxdiff_angle_beta          95.473(3)
_cell_oxdiff_angle_gamma         90.049(3)
_cell_oxdiff_length_a            12.4231(4)
_cell_oxdiff_length_b            17.6736(6)
_cell_oxdiff_length_c            21.3442(6)
_cell_oxdiff_measurement_reflns_used 14913
_cell_oxdiff_volume              4665.0(3)
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.308
_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.a Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C43(H43A,H43B), C35(H35A,H35B), C44(H44A,H44B), C46(H46A,
 H46B), C32(H32A,H32B), C38(H38A,H38B), C34(H34A,H34B), C33(H33A,H33B),
 C45(H45A,H45B), C37(H37A,H37B), C39(H39A,H39B), C36(H36A,H36B), C47(H47A,H47B),
  C28(H28A,H28B), C42(H42A,H42B), C29(H29A,H29B), C41(H41A,H41B), C30(H30A,
 H30B), C31(H31A,H31B)
2.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C13(H13), C7(H7), C16(H16), C25(H25), C4(H4)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C12(H12A,H12B,H12C), C21(H21A,H21B,H21C), C3(H3A,H3B,
 H3C), C9(H9A,H9B,H9C), C27(H27A,H27B,H27C), C15(H15A,H15B,H15C), C24(H24A,H24B,
 H24C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              91943
_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 3.525
_oxdiff_exptl_absorpt_empirical_full_min 0.699