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_1576455
_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
'C36 H30 Fe N3, C18 H36 K N2 O6, 1.5(C4 H8 O), 0.5(C4 H10 O)'
_chemical_formula_sum            'C62 H83 Fe K N5 O8'
_chemical_formula_weight         1121.28
_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             2023-06-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2026-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                114.6990(10)
_cell_angle_beta                 111.7550(10)
_cell_angle_gamma                91.6040(10)
_cell_formula_units_Z            4
_cell_length_a                   17.7676(2)
_cell_length_b                   19.7393(2)
_cell_length_c                   20.0446(2)
_cell_measurement_reflns_used    40237
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.6340
_cell_measurement_theta_min      3.4120
_cell_volume                     5791.04(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.965
_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   -118.00 -33.00   0.50    4.50    --  -47.09 -52.00 104.00  170
  2  \w    -49.00  25.00   0.50    4.50    --  -47.09  52.00-110.00  148
  3  \w    -24.00  61.00   0.50    4.50    --   47.09 -52.00 104.00  170
  4  \w     34.00 120.00   0.50    4.50    --   47.09  52.00-110.00  172
  5  \w    -31.00  26.00   0.50    4.50    --  -47.09  38.00-180.00  114
  6  \w    -55.00  24.00   0.50    4.50    --  -47.09  57.00-120.00  158
  7  \w     -5.00  21.00   0.50    4.50    --  -47.09  19.00-180.00   52
  8  \w    -25.00  29.00   0.50    4.50    --   47.09 -19.00   0.00  108
  9  \w     34.00  89.00   0.50    4.50    --   47.09-125.00 -30.00  110
 10  \w   -163.00 -78.00   0.50   18.00    --  -91.75 -52.00 104.00  170
 11  \w    -49.00 -19.00   0.50   18.00    --  -91.75  52.00-110.00   60
 12  \w   -104.00 -78.00   0.50   18.00    --  -91.75  77.00   0.00   52
 13  \w   -104.00 -79.00   0.50   18.00    --  -91.75 -45.00 -30.00   50
 14  \w    -52.00 -26.00   0.50   18.00    --  -91.75  61.00-150.00   52
 15  \w    -63.00 -22.00   0.50   18.00    --  -91.75  61.00 -30.00   82
 16  \w   -153.00-127.00   0.50   18.00    --  -91.75 -45.00 -30.00   52
 17  \w    -62.00 -19.00   0.50   18.00    --  -91.75  61.00  60.00   86
 18  \w    -62.00 -36.00   0.50   18.00    --  -91.75  77.00   0.00   52
 19  \w     95.00 178.00   0.50   18.00    --  108.41  52.00-110.00  166
 20  \w     36.00  69.00   0.50   18.00    --  108.41 -52.00 104.00   66
 21  \w     78.00 105.00   0.50   18.00    --  108.41 -94.00 -60.00   54
 22  \w     37.00  69.00   0.50   18.00    --  108.41 -94.00 -60.00   64
 23  \w     73.00 105.00   0.50   18.00    --  108.41 -94.00 120.00   64
 24  \w    117.00 178.00   0.50   18.00    --  108.41   0.00 -60.00  122
 25  \w     36.00  89.00   0.50   18.00    --  108.41 -94.00  60.00  106
 26  \w    102.00 178.00   0.50   18.00    --  108.41 125.00  90.00  152
 27  \w     98.00 172.00   0.50   18.00    --  108.41  61.00 150.00  148
 28  \w     44.00 111.00   0.50   18.00    --  108.41-125.00 -90.00  134
 29  \w     41.00  70.00   0.50   18.00    --  108.41 -61.00-120.00   58
 30  \w     44.00  91.00   0.50   18.00    --  108.41-125.00  60.00   94
 31  \w     45.00  74.00   0.50   18.00    --  108.41 -61.00  30.00   58
 32  \w     79.00 128.00   0.50   18.00    --  108.41 -77.00 120.00   98
 33  \w     39.00  71.00   0.50   18.00    --  108.41 -77.00 120.00   64
 34  \w     78.00 104.00   0.50   18.00    --  108.41 -94.00-120.00   52
 35  \w    117.00 177.00   0.50   18.00    --  108.41   0.00-150.00  120
 36  \w     96.00 160.00   0.50   18.00    --  108.41  45.00 120.00  128
 37  \w     36.00 105.00   0.50   18.00    --  108.41 -94.00   0.00  138
 38  \w    123.00 149.00   0.50   18.00    --  108.41   0.00-120.00   52
 39  \w    115.00 178.00   0.50   18.00    --  108.41   0.00  60.00  126
 40  \w     97.00 153.00   0.50   18.00    --  108.41  45.00-180.00  112
 41  \w     36.00 103.00   0.50   18.00    --  108.41 -94.00  90.00  134
 42  \w     57.00 104.00   0.50   18.00    --  108.41 -94.00  30.00   94
 43  \w     59.00 110.00   0.50   18.00    --  108.41-125.00-120.00  102
;
_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      -0.0553220000
_diffrn_orient_matrix_UB_12      -0.0557957000
_diffrn_orient_matrix_UB_13      0.0070947000
_diffrn_orient_matrix_UB_21      -0.0765368000
_diffrn_orient_matrix_UB_22      0.0031453000
_diffrn_orient_matrix_UB_23      -0.0668846000
_diffrn_orient_matrix_UB_31      0.0150435000
_diffrn_orient_matrix_UB_32      -0.0679708000
_diffrn_orient_matrix_UB_33      -0.0646077000
_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  0.0335
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            89789
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.978
_diffrn_reflns_theta_min         3.301
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.200
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88290
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             2396
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.545
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1559
_refine_ls_number_reflns         23903
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0583
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0561P)^2^+6.6799P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1297
_refine_ls_wR_factor_ref         0.1351
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20234
_reflns_number_total             23903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08832a2.cif
_cod_data_source_block           neiar24
_cod_depositor_comments
'Adding full bibliography for 1576451--1576463.cif.'
_cod_original_cell_volume        5791.03(12)
_cod_database_code               1576455
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.831
_shelx_estimated_absorpt_t_min   0.659
_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
 O8-C95 \\sim O8-C95'
 with sigma of 0.02
 O9-C99 \\sim O9-C99'
 with sigma of 0.02
 O10-C100 \\sim O10'-C00'
 with sigma of 0.02
 O10-C101 \\sim O10'-C01'
 with sigma of 0.02
 O11-C105 \\sim O11-C05'
 with sigma of 0.02
 O12-C106 \\sim O12'-C06'
 with sigma of 0.02
 O12-C107 \\sim O12'-C07'
 with sigma of 0.02
 N10-C96 \\sim N10'-C96'
 with sigma of 0.02
 N10-C102 \\sim N10'-C02'
 with sigma of 0.02
 N10-C108 \\sim N10'-C08'
 with sigma of 0.02
 C95-C96 \\sim C95'-C96'
 with sigma of 0.02
 C99-C100 \\sim C99'-C00'
 with sigma of 0.02
 C101-C102 \\sim C01'-C02'
 with sigma of 0.02
 C105-C106 \\sim C05'-C06'
 with sigma of 0.02
 C107-C108 \\sim C07'-C08'
 with sigma of 0.02
 O8-C96 \\sim O8-C96'
 with sigma of 0.04
 O9-C100 \\sim O9-C00'
 with sigma of 0.04
 O10-C99 \\sim O10'-C99'
 with sigma of 0.04
 O10-C102 \\sim O10'-C02'
 with sigma of 0.04
 O11-C106 \\sim O11-C06'
 with sigma of 0.04
 O12-C105 \\sim O12'-C05'
 with sigma of 0.04
 O12-C108 \\sim O12'-C08'
 with sigma of 0.04
 N10-C95 \\sim N10'-C95'
 with sigma of 0.04
 N10-C101 \\sim N10'-C01'
 with sigma of 0.04
 N10-C107 \\sim N10'-C07'
 with sigma of 0.04
 C96-C102 \\sim C96'-C02'
 with sigma of 0.04
 C96-C108 \\sim C96'-C08'
 with sigma of 0.04
 C100-C101 \\sim C00'-C01'
 with sigma of 0.04
 C102-C108 \\sim C02'-C08'
 with sigma of 0.04
 C106-C107 \\sim C06'-C07'
 with sigma of 0.04
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
{O15, C120, C119, C118, C117} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15, C117, C118, C119, C120}
{O15, C117, C118, C119, C120} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15', C17', C18', C19', C20'}
5. Others
 Sof(O15')=Sof(C17')=Sof(H17A)=Sof(H17B)=Sof(C18')=Sof(H18A)=Sof(H18B)=
 Sof(C19')=Sof(H19A)=Sof(H19B)=Sof(C20')=Sof(H20A)=Sof(H20B)=1-FVAR(1)
 Sof(O15)=Sof(C117)=Sof(H11G)=Sof(H11H)=Sof(C118)=Sof(H11I)=Sof(H11J)=
 Sof(C119)=Sof(H11K)=Sof(H11L)=Sof(C120)=Sof(H12N)=Sof(H12O)=FVAR(1)
 Sof(O10')=Sof(O12')=Sof(N10')=Sof(C00')=Sof(H00A)=Sof(H00B)=Sof(C01')=
 Sof(H01A)=Sof(H01B)=Sof(C02')=Sof(H02A)=Sof(H02B)=Sof(C05')=Sof(H05A)=
 Sof(H05B)=Sof(C06')=Sof(H06A)=Sof(H06B)=Sof(C07')=Sof(H07A)=Sof(H07B)=
 Sof(C08')=Sof(H08A)=Sof(H08B)=Sof(C95')=Sof(H95A)=Sof(H95B)=Sof(C96')=
 Sof(H96A)=Sof(H96B)=Sof(C99')=Sof(H99C)=Sof(H99D)=1-FVAR(2)
 Sof(O10)=Sof(O12)=Sof(N10)=Sof(C95)=Sof(H95C)=Sof(H95D)=Sof(C96)=Sof(H96C)=
 Sof(H96D)=Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(C101)=
 Sof(H10C)=Sof(H10D)=Sof(C102)=Sof(H10E)=Sof(H10F)=Sof(C105)=Sof(H10K)=
 Sof(H10L)=Sof(C106)=Sof(H10M)=Sof(H10N)=Sof(C107)=Sof(H10O)=Sof(H10P)=
 Sof(C108)=Sof(H10Q)=Sof(H10R)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,
 H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B),
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B),
  C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C00'(H00A,
 H00B), C01'(H01A,H01B), C02'(H02A,H02B), C05'(H05A,H05B), C06'(H06A,H06B),
 C07'(H07A,H07B), C08'(H08A,H08B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,
 H93B), C94(H94A,H94B), C95'(H95A,H95B), C95(H95C,H95D), C96'(H96A,H96B),
 C96(H96C,H96D), C97(H97A,H97B), C98(H98A,H98B), C99(H99A,H99B), C99'(H99C,
 H99D), C100(H10A,H10B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,H10H),
 C104(H10I,H10J), C105(H10K,H10L), C106(H10M,H10N), C107(H10O,H10P), C108(H10Q,
 H10R), C109(H10S,H10T), C110(H11A,H11B), C111(H11C,H11D), C112(H11E,H11F),
 C17'(H17A,H17B), C18'(H18A,H18B), C19'(H19A,H19B), C20'(H20A,H20B), C117(H11G,
 H11H), C118(H11I,H11J), C119(H11K,H11L), C120(H12N,H12O), C113(H11M,H11N),
 C114(H11O,H11P), C115(H11Q,H11R), C116(H11S,H11T), C122(H12G,H12H), C123(H12I,
 H12J)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26), C28(H28),
  C29(H29), C32(H32), C33(H33), C34(H34), C35(H35), C38(H38), C40(H40),
 C41(H41), C44(H44), C45(H45), C46(H46), C47(H47), C50(H50), C52(H52), C53(H53),
  C56(H56), C57(H57), C58(H58), C59(H59), C62(H62), C64(H64), C65(H65),
 C68(H68), C69(H69), C70(H70), C71(H71)
6.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C36(H36A,H36B,H36C), C48(H48A,H48B,
 H48C), C60(H60A,H60B,H60C), C72(H72A,H72B,H72C), C121(H12D,H12E,H12F),
 C124(H12K,H12L,H12M)
;
_shelx_res_checksum              2829
_olex2_submission_original_sample_id neiar24
_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 1.378
_oxdiff_exptl_absorpt_empirical_full_min 0.842