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_1576994
_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 N4 Rb2'
_chemical_formula_sum            'C70 H94 Fe2 N4 Rb2'
_chemical_formula_weight         1274.13
_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                66.204(4)
_cell_angle_beta                 66.310(4)
_cell_angle_gamma                62.018(4)
_cell_formula_units_Z            1
_cell_length_a                   12.3100(4)
_cell_length_b                   12.4451(4)
_cell_length_c                   13.6698(6)
_cell_measurement_reflns_used    16112
_cell_measurement_temperature    99.98(16)
_cell_measurement_theta_max      30.0510
_cell_measurement_theta_min      3.1940
_cell_volume                     1632.61(13)
_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      99.98(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.855
_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     22.00  89.00   0.50   18.20    --    2.00  72.00 120.00  134
  2  \w    -28.00  19.00   0.50   18.20    --    2.00  72.00 120.00   94
  3  \w    -21.00  79.00   0.50   18.20    --    2.00  57.00 -60.00  200
  4  \w    -33.00   6.00   0.50   18.20    --   -2.40  28.00 -11.88   78
  5  \w    -33.00  72.00   0.50   18.20    --   -2.40  26.00  59.90  210
  6  \w    -33.00  24.00   0.50   18.20    --   -2.40  72.00  60.00  114
  7  \w    -33.00  87.00   0.50   18.20    --   -2.40  28.00-139.26  240
  8  \w     54.00  87.00   0.50   18.20    --   -2.40  72.00-120.00   66
  9  \w    -33.00  32.00   0.50   18.20    --   -2.40  72.00-120.00  130
 10  \w     40.00  86.00   0.50   18.20    --   -2.40  28.00 -11.88   92
 11  \w     47.00  86.00   0.50   18.20    --   -2.40  27.00 167.27   78
 12  \w    -34.00  42.00   0.50   18.20    --   -2.40  27.00 167.27  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0338187000
_diffrn_orient_matrix_UB_12      0.0608467000
_diffrn_orient_matrix_UB_13      0.0094244000
_diffrn_orient_matrix_UB_21      -0.0183887000
_diffrn_orient_matrix_UB_22      -0.0278509000
_diffrn_orient_matrix_UB_23      0.0577068000
_diffrn_orient_matrix_UB_31      0.0556039000
_diffrn_orient_matrix_UB_32      -0.0020453000
_diffrn_orient_matrix_UB_33      0.0060140000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0992
_diffrn_reflns_av_unetI/netI     0.0772
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.855
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            44303
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.242
_diffrn_reflns_theta_min         2.876
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.968
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68445
_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    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.123
_refine_diff_density_min         -0.803
_refine_diff_density_rms         0.128
_refine_ls_extinction_coef       0.0043(10)
_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   1.212
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         8336
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.212
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0626
_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^)+(0.0281P)^2^+7.4452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1535
_refine_ls_wR_factor_ref         0.1610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6160
_reflns_number_total             8336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01470d2.cif
_cod_data_source_block           007c-24010
_cod_depositor_comments
'Adding full bibliography for 1576987--1576994.cif.'
_cod_database_code               1576994
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'Fe C N Rb H'
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.813
_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:
 C33(H33), C18(H18), C30(H30), C21(H21)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C14(H14), C28(H28), C11(H11), C26(H26), C15(H15), C2(H2), C27(H27),
 C7(H7), C10(H10), C8(H8), C9(H9)
2.c Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C4(H4A,H4B,H4C), C19(H19A,H19B,H19C), C35(H35A,H35B,
 H35C), C34(H34A,H34B,H34C), C20(H20A,H20B,H20C), C32(H32A,H32B,H32C), C5(H5A,
 H5B,H5C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              98124
_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 3.129
_oxdiff_exptl_absorpt_empirical_full_min 0.249