Alkali Metal Cation Effects for Rapid C–H Activation by Iron(0) Complexes
Hidalgo, Nereida; Southwell, Kendal W.; Donnelly, Ryan; Mercado, Brandon Q.; Krajewski, Sebastian M.; Wang, Xiaoping; Holland, Patrick L.; Chemical Science  (2026) –; doi:10.1039/D6SC01470D

data_1576991
_publ_section_title
;
 Alkali metal cation effects for rapid C-H activation by iron(0)
 complexes.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              10061
_journal_page_last               10066
_journal_paper_doi               10.1039/d6sc01470d
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C70 H94 Fe2 K2 N4'
_chemical_formula_sum            'C70 H94 Fe2 K2 N4'
_chemical_formula_weight         1181.39
_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
_audit_creation_date             2025-10-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-16 deposited with the CCDC.	2026-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                66.048(3)
_cell_angle_beta                 65.925(3)
_cell_angle_gamma                62.061(3)
_cell_formula_units_Z            1
_cell_length_a                   12.3196(3)
_cell_length_b                   12.4076(3)
_cell_length_c                   13.5563(4)
_cell_measurement_reflns_used    20999
_cell_measurement_temperature    108.7(3)
_cell_measurement_theta_max      76.9130
_cell_measurement_theta_min      3.6950
_cell_volume                     1611.03(9)
_computing_cell_refinement       'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.112a 64-bit (release 01-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_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      108.7(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_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    -11.00  44.00   0.50    0.64    --   46.24 -85.00  75.00  110
  2  \w    -77.00   7.00   0.50    0.64    --  -47.05  85.00-165.00  168
  3  \w   -134.00-101.00   0.50    2.56    --  -84.13 -85.00  75.00   66
  4  \w   -120.00 -16.00   0.50    2.56    --  -84.13  85.00-165.00  208
  5  \w     41.00 108.00   0.50    2.56    --  110.65 -85.00  75.00  134
  6  \w    115.00 140.00   0.50    2.56    --  110.65  85.00-165.00   50
  7  \w    -62.00 -23.00   0.50    0.64    --    0.00 132.00  54.16   78
  8  \w    -43.00 -17.00   0.50    0.64    --   16.00 132.00  54.16   52
  9  \w     -2.00  29.00   0.50    0.64    --   40.00  96.00   3.13   62
 10  \w   -122.00 -74.00   0.50    0.64    --  -47.05-125.00 120.00   96
 11  \w   -129.00 -63.00   0.50    0.64    --  -47.05 -19.00-180.00  132
 12  \w    -47.00  16.00   0.50    0.64    --  -47.05 -19.00-180.00  126
 13  \w      7.00  32.00   0.50    0.64    --   48.00  94.00-118.93   50
 14  \w      8.00  33.00   0.50    0.64    --   48.00  92.00 144.75   50
 15  \w     16.00  41.00   0.50    0.64    --   52.00  85.00  38.25   50
 16  \w     17.00  42.00   0.50    0.64    --   56.00  90.00-175.12   50
 17  \w     17.00  42.00   0.50    0.64    --   56.00  90.00  54.05   50
 18  \w     17.00  43.00   0.50    0.64    --   56.00  90.00-103.71   52
 19  \w     17.00  42.00   0.50    0.64    --   56.00  90.00  99.05   50
 20  \w     17.00  42.00   0.50    0.64    --   56.00  90.00 -43.86   50
 21  \w    -54.00 -29.00   0.50    0.64    --  -60.00 -77.00 120.78   50
 22  \w   -108.00 -83.00   0.50    0.64    --  -60.00 -77.00 120.78   50
 23  \w     35.00  82.00   0.50    0.64    --   64.00  75.00  43.25   94
 24  \w     34.00  70.00   0.50    0.64    --   64.00  76.00 -37.08   72
 25  \w    114.00 139.00   0.50    0.64    --   68.00  77.00  76.37   50
 26  \w     37.00  88.00   0.50    0.64    --   68.00  77.00  76.37  102
 27  \w     99.00 124.00   0.50    0.64    --   68.00  76.00-105.41   50
 28  \w     39.00  65.00   0.50    0.64    --   68.00  76.00-105.41   52
 29  \w     40.00  79.00   0.50    0.64    --   68.00  77.00 100.94   78
 30  \w    -78.00 -44.00   0.50    0.64    --  -72.00 -73.00  88.81   68
 31  \w    -71.00 -45.00   0.50    0.64    --  -76.00 -77.00-174.68   52
 32  \w    -80.00 -49.00   0.50    0.64    --  -76.00 -69.00 107.49   62
 33  \w    -81.00 -46.00   0.50    0.64    --  -76.00 -77.00 155.98   70
 34  \w   -143.00-117.00   0.50    0.64    --  -76.00 -77.00-174.68   52
 35  \w    -72.00 -46.00   0.50    0.64    --  -76.00 -76.00 -26.60   52
 36  \w    -81.00 -53.00   0.50    0.64    --  -80.00 -73.00 -64.12   56
 37  \w    -79.00 -53.00   0.50    0.64    --  -80.00 -71.00-100.55   52
 38  \w   -151.00-125.00   0.50    0.64    --  -80.00 -76.00   5.32   52
 39  \w    -75.00 -49.00   0.50    0.64    --  -80.00 -76.00   5.32   52
 40  \w    -78.00 -52.00   0.50    0.64    --  -80.00 -73.00-149.34   52
 41  \w    -82.00 -49.00   0.50    0.64    --  -80.00 -77.00-116.37   66
 42  \w    -81.00 -55.00   0.50    2.56    --  -84.13 -77.00 150.00   52
 43  \w   -101.00 -35.00   0.50    2.56    --  -84.13  77.00  60.00  132
 44  \w   -102.00 -40.00   0.50    2.56    --  -84.13  77.00   0.00  124
 45  \w    -78.00 -53.00   0.50    2.56    --  -84.13 -77.00   0.00   50
 46  \w    -82.00 -56.00   0.50    2.56    --  -84.13 -77.00 -30.00   52
 47  \w    -87.00 -58.00   0.50    2.56    --  -88.00 -74.00 -72.72   58
 48  \w    -91.00 -57.00   0.50    2.56    --  -88.00 -77.00-172.97   68
 49  \w    -91.00 -62.00   0.50    2.56    --  -92.25 -76.00  80.61   58
 50  \w   -147.00-122.00   0.50    2.56    --  -92.25 -70.00  20.59   50
 51  \w    -90.00 -64.00   0.50    2.56    --  -92.25 -76.00 -77.11   52
 52  \w   -160.00 -95.00   0.50    2.56    --  -92.25 -76.00 -77.11  130
 53  \w    -96.00 -66.00   0.50    2.56    --  -92.25 -71.00 -47.05   60
 54  \w   -149.00-123.00   0.50    2.56    --  -92.25 -71.00 -47.05   52
 55  \w    -91.00 -65.00   0.50    2.56    --  -92.25 -69.00  55.34   52
 56  \w    -86.00 -61.00   0.50    2.56    --  -92.25 -77.00 102.24   50
 57  \w   -163.00-125.00   0.50    2.56    --  -92.25 -77.00 102.24   76
 58  \w   -163.00 -63.00   0.50    2.56    --  -92.25 -73.00-130.48  200
 59  \w   -164.00 -65.00   0.50    2.56    --  -92.25 -69.00 169.28  198
 60  \w   -116.00 -65.00   0.50    2.56    --  -92.25 -70.00  20.59  102
 61  \w   -164.00 -64.00   0.50    2.56    --  -92.25 -71.00 -17.50  200
 62  \w    -91.00 -65.00   0.50    2.56    --  -92.25 -71.00  41.01   52
 63  \w   -160.00 -61.00   0.50    2.56    --  -92.25 -77.00 123.36  198
 64  \w     87.00 136.00   0.50    2.56    --  110.65  61.00 -90.00   98
 65  \w     85.00 174.00   0.50    2.56    --  110.65  77.00  90.00  178
 66  \w     76.00 104.00   0.50    2.56    --  110.65 -95.00 -60.00   56
 67  \w     39.00  70.00   0.50    2.56    --  110.65 -95.00 -60.00   62
 68  \w     86.00 113.00   0.50    2.56    --  110.65  61.00 -30.00   54
 69  \w     80.00 105.00   0.50    2.56    --  110.65 -95.00-150.00   50
 70  \w     37.00  75.00   0.50    2.56    --  110.65 -95.00-150.00   76
 71  \w     80.00 174.00   0.50    2.56    --  110.65  77.00 -90.00  188
 72  \w     80.00 110.00   0.50    2.56    --  110.65  77.00 -30.00   60
 73  \w     36.00  71.00   0.50    2.56    --  110.65 -61.00 -30.00   70
 74  \w     38.00  79.00   0.50    2.56    --  110.65 -95.00  60.00   82
 75  \w    112.00 162.00   0.50    2.56    --  110.65  77.00  60.00  100
 76  \w     49.00 103.00   0.50    2.56    --  110.65 -95.00 -90.00  108
 77  \w     80.00 107.00   0.50    2.56    --  110.65  77.00  60.00   54
 78  \w    118.00 177.00   0.50    2.56    --  110.65  77.00 150.00  118
 79  \w     80.00 112.00   0.50    2.56    --  110.65  77.00 150.00   64
 80  \w     81.00 164.00   0.50    2.56    --  110.65  77.00 120.00  166
 81  \w     81.00 166.00   0.50    2.56    --  110.65  77.00   0.00  170
 82  \w     80.00 177.00   0.50    2.56    --  110.65  77.00-150.00  194
 83  \w    100.00 148.00   0.50    2.56    --  110.65  61.00   0.00   96
 84  \w     88.00 174.00   0.50    2.56    --  110.65  61.00-120.00  172
 85  \w     81.00 161.00   0.50    2.56    --  110.65  77.00  30.00  160
 86  \w     73.00 105.00   0.50    2.56    --  110.65 -95.00-180.00   64
 87  \w    134.00 178.00   0.50    2.56    --  110.65  61.00-180.00   88
 88  \w     88.00 113.00   0.50    2.56    --  110.65  61.00-180.00   50
 89  \w     80.00 123.00   0.50    2.56    --  110.65  77.00-180.00   86
 90  \w     40.00 102.00   0.50    2.56    --  110.65 -95.00 150.00  124
 91  \w     62.00 105.00   0.50    2.56    --  110.65 -95.00  30.00   86
 92  \w     45.00 102.00   0.50    2.56    --  110.65 -95.00 120.00  114
 93  \w     38.00  69.00   0.50    2.56    --  110.65 -95.00-180.00   62
 94  \w     52.00 103.00   0.50    2.56    --  110.65 -95.00 -30.00  102
 95  \w     36.00  72.00   0.50    2.56    --  110.65 -61.00-150.00   72
 96  \w     81.00 107.00   0.50    2.56    --  110.65  77.00-120.00   52
 97  \w     90.00 126.00   0.50    2.56    --  110.65  61.00  90.00   72
 98  \w    127.00 164.00   0.50    2.56    --  110.65  61.00 -30.00   74
 99  \w     83.00 163.00   0.50    2.56    --  110.65  77.00 -60.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1381619000
_diffrn_orient_matrix_UB_12      -0.0360639000
_diffrn_orient_matrix_UB_13      -0.0007595000
_diffrn_orient_matrix_UB_21      0.0318448000
_diffrn_orient_matrix_UB_22      -0.1357056000
_diffrn_orient_matrix_UB_23      -0.0002355000
_diffrn_orient_matrix_UB_31      0.0387674000
_diffrn_orient_matrix_UB_32      0.0392986000
_diffrn_orient_matrix_UB_33      -0.1291313000
_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  0.0670
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            45957
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.000
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45709
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.85 (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       plate
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.974
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.113
_refine_ls_extinction_coef       0.0025(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         6833
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0879
_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^)+(0.0498P)^2^+12.5967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2368
_refine_ls_wR_factor_ref         0.2375
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6612
_reflns_number_total             6833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01470d2.cif
_cod_data_source_block           syn-24078
_cod_depositor_comments
'Adding full bibliography for 1576987--1576994.cif.'
_cod_original_cell_volume        1611.03(10)
_cod_database_code               1576991
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H Fe N K'
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.497
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C18(H18), C21(H21), C30(H30), C33(H33)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15),
 C16(H16), C26(H26), C27(H27), C28(H28)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              34546
_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 1.838
_oxdiff_exptl_absorpt_empirical_full_min 0.579