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_1576993
_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_absolute_configuration ad
_chemical_formula_moiety         'C24 H48 O12 Rb, C31 H45 Fe N2, 1.5(C7 H8)'
_chemical_formula_sum            'C65.5 H105 Fe N2 O12 Rb'
_chemical_formula_weight         1253.83
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-24
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.1945(2)
_cell_length_b                   25.8326(2)
_cell_length_c                   26.0611(2)
_cell_measurement_reflns_used    33531
_cell_measurement_temperature    107.1(4)
_cell_measurement_theta_max      77.2120
_cell_measurement_theta_min      2.7390
_cell_volume                     13595.5(2)
_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      107.1(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.979
_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    -51.00  33.00   0.50    5.99    --  -47.05  47.00 152.00  168
  2  \w   -164.00 -63.00   0.50   23.95    --  -84.13 -47.00   3.00  202
  3  \w    -91.00 -38.00   0.50   23.95    --  -84.13  73.00 -38.00  106
  4  \w    -51.00  -4.00   0.50   23.95    --  -84.13  47.00 152.00   94
  5  \w    -91.00 -38.00   0.50   23.95    --  -84.13  73.00 -38.00  106
  6  \w     49.00  85.00   0.50   23.95    --  110.65-134.00 -46.00   72
  7  \w     96.00 138.00   0.50   23.95    --  110.65  73.00 -38.00   84
  8  \w    122.00 149.00   0.50   23.95    --  110.65 136.00-160.00   54
  9  \w   -119.00 -73.00   0.50    5.99    --  -47.05-125.00  90.00   92
 10  \w    -19.00  35.00   0.50    5.99    --  -47.05  19.00-150.00  108
 11  \w    -33.00  -1.00   0.50   23.95    --  -84.13  30.00 -90.00   64
 12  \w    -33.00  -1.00   0.50   23.95    --  -84.13  30.00 -30.00   64
 13  \w    -31.00  -2.00   0.50   23.95    --  -84.13  30.00 -60.00   58
 14  \w    -33.00  -3.00   0.50   23.95    --  -84.13  30.00  90.00   60
 15  \w    -32.00  -1.00   0.50   23.95    --  -84.13  30.00 120.00   62
 16  \w    -31.00  -1.00   0.50   23.95    --  -84.13  30.00-120.00   60
 17  \w     97.00 178.00   0.50   23.95    --  110.65  45.00 -60.00  162
 18  \w     38.00 102.00   0.50   23.95    --  110.65 -95.00-180.00  128
 19  \w     41.00 100.00   0.50   23.95    --  110.65 -95.00 120.00  118
 20  \w     35.00  61.00   0.50   23.95    --  110.65 -61.00-150.00   52
 21  \w     35.00  73.00   0.50   23.95    --  110.65 -61.00   0.00   76
 22  \w     59.00 102.00   0.50   23.95    --  110.65 -77.00 -30.00   86
 23  \w     35.00  71.00   0.50   23.95    --  110.65 -61.00 120.00   72
 24  \w     97.00 168.00   0.50   23.95    --  110.65  61.00  60.00  142
 25  \w     78.00 103.00   0.50   23.95    --  110.65 -95.00   0.00   50
 26  \w     38.00  96.00   0.50   23.95    --  110.65 -73.00-167.00  116
;
_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      -0.0093918000
_diffrn_orient_matrix_UB_12      -0.0109301000
_diffrn_orient_matrix_UB_13      0.0576675000
_diffrn_orient_matrix_UB_21      -0.0432826000
_diffrn_orient_matrix_UB_22      -0.0472610000
_diffrn_orient_matrix_UB_23      -0.0130907000
_diffrn_orient_matrix_UB_31      0.0620767000
_diffrn_orient_matrix_UB_32      -0.0346930000
_diffrn_orient_matrix_UB_33      -0.0002582000
_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  0.0725
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            104902
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.840
_diffrn_reflns_theta_min         2.408
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.104
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47679
_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    1.225
_exptl_crystal_description       block
_exptl_crystal_F_000             5368
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.838
_refine_diff_density_min         -0.791
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.047(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1526
_refine_ls_number_reflns         28260
_refine_ls_number_restraints     528
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.1268
_refine_ls_R_factor_gt           0.0858
_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^)+(0.0265P)^2^+48.3591P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1611
_refine_ls_wR_factor_ref         0.1812
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                19670
_reflns_number_total             28260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01470d2.cif
_cod_data_source_block           syn-24057
_cod_depositor_comments
'Adding full bibliography for 1576987--1576994.cif.'
_cod_original_formula_sum        'C65.50 H105 Fe N2 O12 Rb'
_cod_database_code               1576993
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C63H98FeN2O11Rb
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.707
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.953(7)
 0.047(7)
2. 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
3. Uiso/Uaniso restraints and constraints
C129 \\sim C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim C137 \\sim
C138 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim C134 \\sim C135: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C129, C124, C125, C126, C127, C128, C137, C138, C130, C131, C132, C133, C134,
 C135
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, O8, O9, O10, O11, O12, C74, C75, C76, C77, C78, C79, C80, C81, C82, C83,
 C84, C85, O13, O14, O15, O16, O17, O18, C86, C87, C88, C89, C90, C91, C92, C93,
  C94, C95, C96, C97
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C138)=Sof(H13C)=Sof(H13D)=Sof(H13E)=Sof(C130)=Sof(C131)=Sof(H131)=
 Sof(C132)=Sof(H132)=Sof(C133)=Sof(H133)=Sof(C134)=Sof(H134)=Sof(C135)=
 Sof(H135)=1-FVAR(1)
 Sof(C129)=Sof(C124)=Sof(C125)=Sof(H125)=Sof(C126)=Sof(H126)=Sof(C127)=
 Sof(H127)=Sof(C128)=Sof(H128)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C137)=
 Sof(H137)=FVAR(1)
6.a Free rotating group:
 C129(C124,C125,H125,C126,H126,C127,H127,C128,H128,H12D,H12E,H12F,C137,H137),
 C138(C130,C131,H131,C132,H132,C133,H133,C134,H134,C135,H135)
6.b Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C26(H26), C29(H29), C45(H45), C48(H48), C57(H57), C60(H60)
6.c Secondary CH2 refined with riding coordinates:
 C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,
 H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B),
 C72(H72A,H72B), 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),
 C136(H13A,H13B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,
 H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B),
 C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B),
  C99(H99A,H99B), 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), C1(H1A,H1B), C2(H2A,H2B), C32(H32A,H32B),
 C33(H33A,H33B)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C11(H11), C12(H12), C22(H22), C23(H23), C24(H24), C35(H35),
 C41(H41), C42(H42), C43(H43), C53(H53), C54(H54), C55(H55), C111(H111),
 C112(H112), C113(H113), C114(H114), C115(H115), C118(H118), C119(H119),
 C120(H120), C121(H121), C122(H122)
6.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C116(H11A,H11B,H11C), C123(H12A,H12B,H12C),
 C138(H13C,H13D,H13E)
;
_shelx_res_checksum              54477
_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 2.254
_oxdiff_exptl_absorpt_empirical_full_min 0.488