Direct metathesis of carbon–carbon σ-bonds at a versatile macrocycle-supported diiron platform
Liu, Tianchang; Gonder, Jared E.; Murphy, Ryan P.; Bacon, Alexandra M.; Gau, Michael R.; Tomson, Neil C.; Chemical Science  (2026) –; doi:10.1039/D5SC10054B

data_1576582
_publ_section_title
;
 Direct metathesis of carbon-carbon <i>&#x3c3;</i>-bonds at a versatile
 macrocycle-supported diiron platform.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              7203
_journal_page_last               7210
_journal_paper_doi               10.1039/d5sc10054b
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C64 H71 Fe2 N6 P, 2(F6 P), 1.5(C6 H5 F)'
_chemical_formula_sum            'C73 H78.5 F13.5 Fe2 N6 P3'
_chemical_formula_weight         1501.02
_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             2024-07-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2024-08-02 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.540(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.4482(3)
_cell_length_b                   11.9450(2)
_cell_length_c                   26.3761(4)
_cell_measurement_reflns_used    68136
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.3130
_cell_measurement_theta_min      1.9550
_cell_volume                     7259.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.91a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-6000HE
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -26.00   0.00   0.50   10.00    --    8.19 -80.00-119.00   52
  2  \w    -31.00  -6.00   0.50   10.00    --   -9.91  80.00   4.00   50
  3  \w    -41.00  10.00   0.50   10.00    --   -9.91 -80.00-119.00  102
  4  \w     -5.00  82.00   0.50   10.00    --    8.19  37.00  90.00  174
  5  \w    -72.00 -46.00   0.50   10.00    --   -9.91 -19.00-150.00   52
  6  \w    -20.00   6.00   0.50   10.00    --   -9.91  78.00 106.90   52
  7  \w    -84.00 -46.00   0.50   10.00    --   -9.91 -77.00 -60.00   76
  8  \w    -29.00  -3.00   0.50   10.00    --   -9.91 -77.00 -60.00   52
  9  \w    -27.00  47.00   0.50   10.00    --   -9.91  76.00 -80.02  148
 10  \w    -83.00   6.00   0.50   10.00    --   -9.91 -57.00 -30.00  178
 11  \w    -26.00  63.00   0.50   10.00    --   -9.91  57.00-150.00  178
 12  \w    -39.00   6.00   0.50   10.00    --   -9.91 -57.00  60.00   90
 13  \w    -13.00  13.00   0.50   10.00    --   -9.91  75.00 -20.95   52
 14  \w     17.00  53.00   0.50   10.00    --   -9.91  75.00 -20.95   72
 15  \w    -34.00  22.00   0.50   10.00    --   -9.91  78.00 128.13  112
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0026403000
_diffrn_orient_matrix_UB_12      -0.0524544000
_diffrn_orient_matrix_UB_13      -0.0132112000
_diffrn_orient_matrix_UB_21      0.0251733000
_diffrn_orient_matrix_UB_22      -0.0193906000
_diffrn_orient_matrix_UB_23      0.0205554000
_diffrn_orient_matrix_UB_31      -0.0175146000
_diffrn_orient_matrix_UB_32      -0.0199652000
_diffrn_orient_matrix_UB_33      0.0147498000
_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  0.0402
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            164937
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         1.891
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.546
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72303
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       plank
_exptl_crystal_F_000             3108
_exptl_crystal_size_max          0.62
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.098
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         17997
_refine_ls_number_restraints     330
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0445
_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^)+(0.0824P)^2^+5.4027P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1324
_refine_ls_wR_factor_ref         0.1373
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15526
_reflns_number_total             17997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc10054b2.cif
_cod_data_source_block           30011_Fe2C=CPh2_2+
_cod_depositor_comments
'Adding full bibliography for 1576580--1576582.cif.'
_cod_original_formula_sum        'C73 H78.50 F13.50 Fe2 N6 P3'
_cod_database_code               1576582
_shelx_shelxl_version_number     2019/3
_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. Uiso/Uaniso restraints and constraints
F14 \\sim C66 \\sim C71 \\sim C70 \\sim C69 \\sim C68 \\sim C67 \\sim F14'
\\sim C66' \\sim C71' \\sim C70' \\sim C69' \\sim C68' \\sim C67' \\sim F14*
\\sim C66* \\sim C67* \\sim C68* \\sim C69* \\sim C70* \\sim C71*: within 2A
with sigma of 0.003 and sigma for terminal atoms of 0.006 within 2A
3. Others
 Fixed Sof: F13(0.75) F13*(0.25) H62(0.25) H65(0.75) F14(0.2) C66(0.2)
 C67(0.2) H67(0.2) C68(0.2) H68(0.2) C69(0.2) H69(0.2) C70(0.2) H70(0.2)
 C71(0.2) H71(0.2) F14'(0.15) C66'(0.15) C67'(0.15) H67'(0.15) C68'(0.15)
 H68'(0.15) C69'(0.15) H69'(0.15) C70'(0.15) H70'(0.15) C71'(0.15) H71'(0.15)
 F14*(0.15) C66*(0.15) C67*(0.15) H67*(0.15) C68*(0.15) H68*(0.15) C69*(0.15)
 H69*(0.15) C70*(0.15) H70*(0.15) C71*(0.15) H71*(0.15)
4.a Free rotating group:
 F14(C66,C67,C68,C69,C70,C71), F14'(C66',C67',C68',C69',C70',C71'), F14*(C66*,
 C67*,C68*,C69*,C70*,C71*)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C13(H13), C15(H15), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57),
 C58(H58), C59(H59), C75(H75), C76(H76), C77(H77), C79(H79), C60(H60), C61(H61),
  C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68), C69(H69),
 C70(H70), C71(H71), C67'(H67'), C68'(H68'), C69'(H69'), C70'(H70'), C71'(H71'),
  C67*(H67*), C68*(H68*), C69*(H69*), C70*(H70*), C71*(H71*)
4.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              91818
_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 1.454
_oxdiff_exptl_absorpt_empirical_full_min 0.648